Supported nonmetallocene catalyst, preparation and use thereof

ABSTRACT

This invention relates to a supported nonmetallocene catalyst and preparation thereof. The supported nonmetallocene catalyst can be produced with a simple and feasible process and is characterized by an easily controllable polymerization activity. This invention further relates to use of the supported nonmetallocene catalyst in olefin homopolymerization/copolymerization, which is characterized by a lowered assumption of the co-catalyst as compared with the prior art.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a U.S. national phase application based onPCT/CN2010/001604, filed Oct. 13, 2010, which claims the priority ofChinese Application Nos. 200910180100.6, filed Oct. 26, 2009;200910180607.1, filed Oct. 26, 2009; 200910180601.4, filed Oct. 26,2009; and 200910180606.7, filed Oct. 26, 2009, the contents of all ofwhich are incorporated by reference herein in their entirety.

TECHNICAL FIELD

The present invention relates to a nonmetallocene catalyst.Specifically, this invention relates to a supported nonmetallocenecatalyst, preparation thereof and use thereof in olefinhomopolymerization/copolymerization.

BACKGROUND ART

The nonmetallocene catalyst, also called as the post-metallocenecatalyst, was discovered in middle and late 1990's, whose central atominvolves nearly all of the transition metal elements. The nonmetallocenecatalyst is comparative to, or exceeds, the metallocene catalyst in someaspects of the performance, and has been classified as the fourthgeneration catalyst for olefin polymerization, following the Zieglercatalyst, the Ziegler-Natta catalyst and the metallocene catalyst.Polyolefin products produced with such catalysts exhibit favorableproperties and boast low production cost. The coordination atom of thenonmetallocene catalyst comprises oxygen, nitrogen, sulfur and phosphor,without containing a cyclopentadiene group or a derivative thereof (forexample, an indene group or a fluorene group). The nonmetallocenecatalyst is characterized in that its central atom shows comparativelystrong electrophilicity and has a cis alkyl metal type or a metal halidetype central structure, which facilitates olefin insertion and σ-bondtransfer. Therefore, the central atom is easily subject to alkylation,and therefore facilitates formation of a cationic active center. Thethus formed complex has a restricted geometrical configuration, and isstereoselective, electronegative and chiral adjustable. Further, theformed metal-carbon bond is easy to be polarized, which furtherfacilitates homopolymerization and copolymerization of an olefin. Forthese reasons, it is possible to obtain an olefin polymer having acomparatively high molecular weight, even under a comparatively highpolymerization temperature.

However, it is known that in the olefin polymerization, the homogeneousphase catalyst suffers from such problems as short service life,fouling, high consumption of methyl aluminoxane, and undesirably low orhigh molecular weight in the polymer product, and thus only findslimited use in the solution polymerization process or the high-pressurepolymerization process, which hinders its wider application in industry.

Chinese patent Nos. 01126323.7, 02151294.9 and 02110844.7, andWO03/010207 disclose a catalyst or catalyst system finding a broadapplication in olefin polymerization. However, the catalyst or catalystsystem should be accompanied by a comparatively high amount ofco-catalysts, to achieve an acceptable olefin polymerization activity.Further, the catalyst or catalyst system suffers from such problems asshort service life and fouling.

It is normal to support the nonmetallocene catalyst by a certainprocess, so as to improve the performance of the catalyst in thepolymerization and the particle morphology of the polymer products. Thisis reflected by, moderate reduction of the initial activity of thecatalyst, elongation of the serve life of the catalyst, alleviation orelimination of caking or flash reaction during the polymerization,improvement of the polymer morphology, and increase of the apparentdensity of the polymer, thus extending its use to other polymerizationprocesses, for example, the gas phase polymerization or the slurrypolymerization.

Aiming at the catalysts of the Chinese patent Nos. 01126323.7,02151294.9 and 02110844.7, and WO03/010207, Chinese patent applicationLaid-Open Nos. CN1539855A, CN1539856A, CN1789291A, CN1789292A andCN1789290A, and WO2006/063501, and Chinese application patent No.200510119401.x provide several ways to support same catalyst on acarrier so as to obtain a supported nonmetallocene catalyst. However,each of these applications relates to the technology of supporting atransition metal-containing nonmetallocene organic metallic compound ona treated carrier, which necessarily involves complicate preparationsteps.

Chinese patent application Laid-Open No. CN1539856A discloses a processfor supporting a nonmetallocene catalyst on a composite carrier,comprising the steps of (1) drying or baking a porous carrier (as thecarrier) at 100 to 1000° C., under an inert atmosphere or under areduced pressure for 1 to 24 hours to thermally activate same; (2)dissolving a magnesium compound in a tetrahydrofuran-alcohol mixingsystem to obtain a solution, and then adding the thermally activatedporous carrier to the solution, to sufficiently react with each other at0 to 60° C. under stirring to obtain a transparent system, uponfiltration, washing, drying and suction drying, to obtain a compositecarrier; or introducing into the transparent solution a non-polarorganic solvent to sufficiently precipitate same, and then uponfiltration, washing, drying and suction drying to obtain a compositecarrier; (3) dissolving a nonmetallocene catalyst for olefinpolymerization in a solvent, and then contacting same with the compositecarrier or the modified carrier for 12 to 72 hours, upon filtration,washing, drying and suction drying, to obtain the supportednonmetallocene catalyst. According to this process, it is necessary toprepare the composite carrier at the first place and then contactingsame with the catalyst solution.

Chinese patent application Laid-Open No. CN1789290A discloses a processfor supporting a nonmetallocene catalyst with a high activity,comprising the steps of reacting a carrier with a chemical activatingagent to obtain a modified carrier; dissolving a magnesium compound in atetrahydrofuran-alcohol mixing system to obtain a solution, and thenadding the modified carrier to the solution to conduct a react, uponfiltration, washing, drying and suction drying, to obtain a compositecarrier; dissolving a nonmetallocene catalyst for olefin polymerizationin a solvent, and then reacting same with the composite carrier, uponfiltration, washing, drying and suction drying, to obtain the supportednonmetallocene catalyst. According to this process, it is necessary toprepare the modified carrier at the first place and then reacting samewith the magnesium compound to obtain the composite carrier and thencontacting same with the catalyst solution.

Chinese patent application Laid-Open No. CN101423574A discloses asupported single site nonmetallocene catalyst component and thepreparation process thereof, comprising the steps of (1) preparation ofa magnesium chloride/silica carrier; (2) preparation of an alkylaluminoxane/magnesium chloride/silica carrier; and (3) preparation ofthe supported single site nonmetallocene catalyst component. Accordingto this process, it is necessary to prepare the composite carrier at thefirst place and then reacting same with the alkyl aluminoxane, andfinally contacting same with the catalyst solution.

Most of the prior art olefin polymerization catalysts are metallocenecatalyst-based, for example, those according to U.S. Pat. No. 4,808,561and U.S. Pat. No. 5,240,894, Chinese patent application Laid-Open Nos.CN1344749A, CN1126480A, CN1307594A, CN1103069A, and CN1363537A, and U.S.Pat. No. 6,444,604, EP 0685494, U.S. Pat. No. 4,871,705 and EP0206794,and Chinese patent No. 94101358.8. Again, all of these applicationsrelate to the technology of supporting a transition metal-containingmetallocene catalyst on a treated carrier.

The catalyst prepared using anhydrous magnesium chloride as a carrierexhibits a high catalytic activity in the olefin polymerization, butthis kind of catalyst is very brittle, prone to crush in thepolymerization reactor, resulting in a poor polymer morphology. Thecatalyst supported on silica has an excellent flowability, useful to afluidized-bed gas-phase polymerization, but the silica-supportedmetallocene and nonmetallocene catalyst shows a lowered catalyticactivity. If magnesium chloride could be appropriately combined withsilica, a catalyst with high catalytic activity, controllable granulesize and good abrasion resistance may be obtained.

According to EP0260130, provided is a catalyst produced by supporting ametallocene or nonmetallocene transition metal compound onto a methylaluminoxane-treated SiO2 carrier, wherein the nonmetallocene transitionmetal herein refers to ZrCl4, TiCl4 or VOCl3 only. According to thispatent, it is preferred for the surface of the carrier to be treatedwith an organic magnesium compound or the mixture of a magnesiumcompound and an alkyl aluminum. However, the process involved is verycomplicated, necessitating a vast of production steps.

Chinese patent No. 200610026765.8 discloses a single site Ziegler-Nattacatalyst for olefin polymerization. In this catalyst, a coordinationgroup-containing salicylaldehyde or substituted salicylaldehydederivative is used as the electron donor. The catalyst is produced byintroducing a pre-treated carrier (for example, silica), a metalliccompound (for example, TiCl4) and the electron donor into a magnesiumcompound (for example, MgCl2)/tetrahydrofuran solution and thenpost-treating the resultant.

Chinese patent No. 200610026766.2 is similar to this patent, and relatesto an organic compound containing a hetero atom and use thereof forproducing a Ziegler-Natta catalyst.

Chinese patent application Laid-Open No. CN101412766A discloses aprocess for producing a magnesium compound supported nonmetallocenecatalyst, comprising the steps of contacting a magnesium compound with anonmetallocene ligand, to obtain a contact resultant, and treating thecontact resultant with a chemical treating agent selected from the groupconsisting of Group IVB metal compounds, to obtain the magnesiumcompound-supported nonmetallocene catalyst. The thus obtained catalystexhibits a relatively higher activity, however, a poor polymer particlemorphology, a rather lowered bulk density and a relatively increasedamount of fine powders.

As can be seen from aforesaid, the prior art supported nonmetallocenecatalyst suffers from such problems as a complicate supporting process,which generally involves multiple steps for treating the carrier beforesupporting the nonmetallocene complex, and a low olefin polymerizationactivity, wherein there is no easy way to adjust same. If one tries toincrease the activity, he has to significantly increase the amount ofthe co-catalyst to be used, which is undesirable. Further, the prior artsupported nonmetallocene catalyst has been produced by supporting anonmetallocene complex onto a treated carrier, and therefore isproblematic in stability.

Therefore, there still exists a need for a supported nonmetallocenecatalyst, which can be produced in a simple way and in an industrialscale, free of the problems associated with the prior art supportednonmetallocene catalyst.

SUMMARY OF THE INVENTION

Upon in-depth study of the prior art, the present inventors found that asupported nonmetallocene catalyst produced by using a specific processcan solve the problems identified as aforesaid, whereby achieving thisinvention.

According to this invention, the present process for producing asupported nonmetallocene catalyst can be conducted in the absence of anyproton donor or any electron donor (for example, di-ether compoundsconventionally used in this field for this purpose), without the need ofsevere reaction requirements and reaction conditions. For these reasons,the present process is simple and suitable for industrial application.

Specifically, this invention generally relates to the first to fourthembodiments as follows.

The first embodiment relates to a process for producing a supportednonmetallocene catalyst, which comprises the steps of: dissolving amagnesium compound and a nonmetallocene complex in a solvent, to obtaina magnesium compound solution; mixing a porous carrier or a thermallyactivated porous carrier with the magnesium compound solution to obtaina slurry; and drying the slurry to obtain the supported nonmetallocenecatalyst.

The second embodiment relates to a process for producing a supportednonmetallocene catalyst, which comprises the steps of: dissolving amagnesium compound and a nonmetallocene complex in a solvent, to obtaina magnesium compound solution; mixing a porous carrier or a thermallyactivated porous carrier with the magnesium compound solution to obtaina slurry; and introducing into the slurry a precipitating agent toobtain the supported nonmetallocene catalyst.

The third embodiment relates to a process for producing a supportednonmetallocene catalyst, which comprises the steps of: dissolving amagnesium compound and a nonmetallocene complex in a solvent, to obtaina magnesium compound solution; mixing a porous carrier or a thermallyactivated porous carrier with the magnesium compound solution to obtaina slurry; drying the slurry to obtain a composite carrier; and treatingthe composite carrier with a chemical treating agent selected from thegroup consisting of Group IVB metal compounds to obtain the supportednonmetallocene catalyst.

The fourth embodiment relates to a process for producing a supportednonmetallocene catalyst, which comprises the steps of: dissolving amagnesium compound and a nonmetallocene complex in a solvent, to obtaina magnesium compound solution; mixing a porous carrier or a thermallyactivated porous carrier with the magnesium compound solution to obtaina slurry; introducing into the slurry a precipitating agent to obtain acomposite carrier; and treating the composite carrier with a chemicaltreating agent selected from the group consisting of Group IVB metalcompounds to obtain the supported nonmetallocene catalyst.

More specifically, this invention relates to the following aspects.

1. A process for producing a supported nonmetallocene catalyst,comprising the steps of: dissolving a magnesium compound and anonmetallocene complex in a solvent, to obtain a magnesium compoundsolution; mixing a porous carrier or a thermally activated porouscarrier with the magnesium compound solution to obtain a slurry; anddrying the slurry, or introducing into the slurry a precipitating agent,to obtain the supported nonmetallocene catalyst.

2. A process for producing a supported nonmetallocene catalyst,comprising the steps of: dissolving a magnesium compound and anonmetallocene complex in a solvent, to obtain a magnesium compoundsolution; mixing a porous carrier or a thermally activated porouscarrier with the magnesium compound solution to obtain a slurry; dryingthe slurry, or introducing into the slurry a precipitating agent, toobtain a composite carrier; and treating the composite carrier with achemical treating agent selected from the group consisting of a GroupIVB metal compound to obtain the supported nonmetallocene catalyst.

3. The process according to any of the aforesaid aspects, furthercomprising the step of pre-treating the composite carrier with anassistant chemical treating agent selected from the group consisting ofan aluminoxane, an alkylaluminum and any combination thereof beforetreating the composite carrier with the chemical treating agent.

4. The process according to any of the aforesaid aspects, wherein theporous carrier is one or more selected from the group consisting ofolefin homopolymers or copolymers, vinyl alcohol homopolymers orcopolymers, cyclodextrins, polyesters or co-polyesters, polyamides orco-polyamides, vinyl chloride homopolymers or copolymers, acrylic esterhomopolymers or copolymers, methacrylic ester homopolymers orcopolymers, styrene homopolymers or copolymers, partly crosslinkedproducts of these homopolymers or copolymers, refractory oxides orrefractory composite oxides of a Group IIA, IIIA, IVA or IVB metal inthe Periodic Table of Elements, clay, molecular sieve, mica,montmorillonite, bentonite and kieselguhr, preferably one or moreselected from the group consisting of partly crosslinked styrenepolymers, silica, alumina, magnesia, silica-alumina, magnesia-alumina,titanium oxide, molecular sieve and montmorillonite, more preferablysilica, and/or the magnesium compound is one or more selected from thegroup consisting of a magnesium halide, an alkoxy magnesium halide, analkoxy magnesium, an alkyl magnesium, an alkyl magnesium halide and analkyl alkoxy magnesium, preferably one or more selected from the groupconsisting of a magnesium halide, more preferably magnesium chloride.

5. The process according to any of the aforesaid aspects, wherein thesolvent is one or more selected from the group consisting of a C₆₋₁₂aromatic hydrocarbon, a halogenated C₆₋₁₂ aromatic hydrocarbon, an esterand an ether, preferably one or more selected from the group consistingof a C₆₋₁₂ aromatic hydrocarbon and tetrahydrofuran, more preferablytetrahydrofuran.

6. The process according to any of the aforesaid aspects, wherein thenonmetallocene complex is one or more selected from the group consistingof the compounds having the following structure,

preferably one or more selected from the group consisting of thefollowing compound (A) and the following compound (B),

more preferably one or more selected from the group consisting of thefollowing compound (A-1), the following compound (A-2), the followingcompound (A-3), the following compound (A-4), the following compound(B-1), the following compound (B-2), the following compound (B-3), andthe following compound (B-4),

in all of the aforesaid formulae,

q is 0 or 1;

d is 0 or 1;

m is 1, 2 or 3;

M is selected from the group consisting of a Group III to XI metal atomin the Periodic Table of Elements, preferably from the group consistingof a Group IVB metal atom, more preferably from the group consisting ofTi(IV) and Zr(IV);

n is 1, 2, 3 or 4, depending on the valence of the central metal atom M;

X is selected from the group consisting of a halogen atom, a hydrogenatom, a C₁-C₃₀ hydrocarbyl, a substituted C₁-C₃₀ hydrocarbyl, anoxygen-containing group, a nitrogen-containing group, asulfur-containing group, a boron-containing group, analuminium-containing group, a phosphor-containing group, asilicon-containing group, a germanium-containing group, and atin-containing group, when multiple Xs exist, the Xs may be the same asor different from one another, and may form a bond or a ring with oneanother;

A is selected from the group consisting of an oxygen atom, a sulfuratom, a selenium atom,

—NR²³R²⁴, —N(O)R²⁵R²⁶,

—PR²⁸R²⁹, —P(O)R³⁰OR³¹, a sulfone group, a sulfoxide group and—Se(O)R³⁹, wherein N, O, S, Se and P each represents a coordinationatom;

B is selected from the group consisting of a nitrogen atom, anitrogen-containing group, a phosphor-containing group and a C₁-C₃₀hydrocarbyl;

D is selected from the group consisting of a nitrogen atom, an oxygenatom, a sulfur atom, a selenium atom, a phosphor atom, anitrogen-containing group, a phosphor-containing group, a C₁-C₃₀hydrocarbyl, a sulfone group, a sulfoxide group,

—N(O)R²⁵R²⁶,

and —P(O)R³²(OR³³), wherein N, O, S, Se and P each represents acoordination atom;

E is selected from the group consisting of a nitrogen-containing group,an oxygen-containing group, a sulfur-containing group, aselenium-containing group, a phosphor-containing group and a cyanogroup, wherein N, O, S, Se and P each represents a coordination atom;

F is selected from the group consisting of a nitrogen atom, anitrogen-containing group, an oxygen-containing group, asulfur-containing group, a selenium-containing group and aphosphor-containing group, wherein N, O, S, Se and P each represents acoordination atom;

G is selected from the group consisting of a C₁-C₃₀ hydrocarbyl, asubstituted C₁-C₃₀ hydrocarbyl and an inert functional group;

Y is selected from the group consisting of an oxygen atom, anitrogen-containing group, an oxygen-containing group, asulfur-containing group, a selenium-containing group and aphosphor-containing group, wherein N, O, S, Se and P each represents acoordination atom;

Z is selected from the group consisting of a nitrogen-containing group,an oxygen-containing group, a sulfur-containing group, aselenium-containing group, a phosphor-containing group and a cyanogroup, wherein N, O, S, Se and P each represents a coordination atom;

→ represents a single bond or a double bond;

- represents a covalent bond or an ionic bond;

--- represents a coordination bond, a covalent bond or an ionic bond;

R¹ to R⁴, R⁶ to R³⁶, R³⁸ and R³⁹ are each independently selected fromthe group consisting of a hydrogen atom, a C₁-C₃₀ hydrocarbyl, asubstituted C₁-C₃₀ hydrocarbyl and an inert functional group, whereinthese groups may be identical to or different from one another, and anyadjacent groups may form a bond or a ring (preferably an aromatic ring)with one another; and

R⁵ is selected from the group consisting of the lone pair electron onthe nitrogen atom, a hydrogen atom, a C₁-C₃₀ hydrocarbyl, a substitutedC₁-C₃₀ hydrocarbyl, an oxygen-containing group, a sulfur-containinggroup, a nitrogen-containing group, a selenium-containing group, and aphosphor-containing group, with the proviso that when R⁵ is theoxygen-containing group, the sulfur-containing group, thenitrogen-containing group, the selenium-containing group or thephosphor-containing group, N, O, S, P and Se in the group R⁵ each canact as a coordination atom to coordinate with the central metal atom(the Group IVB metal atom),

more preferably one or more selected from the group consisting of thefollowing compounds,

more preferably one or more selected from the group consisting of thefollowing compounds,

7. The process according to any of the aforesaid aspects, wherein, thehalogen atom is selected from the group consisting of F, Cl, Br and I,group is selected from the group consisting of

—NR²³R²⁴, -T-NR²³R²⁴ and —N(O)R²⁵R²⁶,

the phosphor-containing group is selected from the group consisting of

—PR²⁸R²⁹, —P(O)R³⁰R³¹ and —P(O)R³²(OR³³),

the oxygen-containing group is selected from the group consisting ofhydroxy, —OR³⁴ and -T-OR³⁴,

the sulfur-containing group is selected from the group consisting of—SR³⁵, -T-SR³⁵, —S(O)R³⁶ and -T-SO₂R³⁷,

the selenium-containing group is selected from the group consisting of—SeR³⁸, -T-SeR³⁸, —Se(O)R³⁹ and -T-Se(O)R³⁹,

the group T is selected from the group consisting of a C₁-C₃₀hydrocarbyl, a substituted C₁-C₃₀ hydrocarbyl and an inert functionalgroup,

R³⁷ is selected from the group consisting of a hydrogen atom, a C₁-C₃₀hydrocarbyl, a substituted C₁-C₃₀ hydrocarbyl and an inert functionalgroup,

the C₁-C₃₀ hydrocarbyl is selected from the group consisting of a C₁-C₃₀alkyl group, a C₇-C₅₀ alkylaryl group, a C₇-C₅₀ aralkyl group, a C₃-C₃₀cyclic alkyl group, a C₂-C₃₀ alkenyl group, a C₂-C₃₀ alkynyl group, aC₆-C₃₀ aryl group, a C₈-C₃₀ fused-ring group and a C₄-C₃₀ heterocyclegroup, wherein the heterocycle group contains 1 to 3 hetero atom(s)selected from the group consisting of a nitrogen atom, an oxygen atomand a sulfur atom,

the substituted C₁-C₃₀ hydrocarbyl is selected from the group consistingof the C₁-C₃₀ hydrocarbyl having one or more substituent(s) selectedfrom the halogen atom and the C₁-C₃₀ alkyl group,

the inert functional group is selected from the group consisting of thehalogen atom, the oxygen-containing group, the nitrogen-containinggroup, a silicon-containing group, a germanium-containing group, thesulfur-containing group, a tin-containing group, a C₁-C₁₀ ester groupand a nitro group,

the boron-containing group is selected from the group consisting of BF₄⁻, (C₆F₅)₄B⁻ and (R⁴⁰BAr₃)⁻,

the aluminium-containing group is selected from the group consisting ofan alkyl aluminium, AlPh₄ ⁻, AlF₄ ⁻, AlCl₄ ⁻, AlBr₄ ⁻, AlI₄ ⁻ andR⁴¹AlAr₃,

the silicon-containing group is selected from the group consisting of—SiR⁴²R⁴³R⁴⁴, and -T-SiR⁴⁵,

the germanium-containing group is selected from the group consisting of—GeR⁴⁵R⁴⁷R⁴⁸, and -T-GeR⁴⁹,

the tin-containing group is selected from the group consisting of—SnR⁵⁰R⁵¹R⁵², -T-SnR⁵³ and -T-Sn(O)R⁵⁴,

the Ar group represents a C₆-C₃₀ aryl group,

R⁴⁰ to R⁵⁴ are each independently selected from the group consisting ofa hydrogen atom, the C₁-C₃₀ hydrocarbyl, the substituted C₁-C₃₀hydrocarbyl and the inert functional group, wherein these groups may beidentical to or different from one another, and any adjacent groups mayform a bond or a ring with one another, and

the group T is defined as aforesaid.

8. The process according to any of the aforesaid aspects, wherein ratioby molar of the magnesium compound (based on Mg) to the nonmetallocenecomplex is 1:0.01-1, preferably 1:0.04-0.4, more preferably 1:0.08-0.2,ratio of the magnesium compound to the solvent is 1 mol:75˜400 ml,preferably 1 mol:150˜300 ml, more preferably 1 mol:200˜250 ml, ratio byweight of the magnesium compound (on a solid basis) to the porouscarrier is 1:0.1-20, preferably 1:0.5-10, more preferably 1:1-5, andratio by volume of the precipitating agent to the solvent is 1:0.2˜5,preferably 1:0.5˜2, more preferably 1:0.8˜1.5.

9. The process according to any of the aforesaid aspects, wherein ratioby molar of the magnesium compound (based on Mg) to the nonmetallocenecomplex is 1:0.01-1, preferably 1:0.04-0.4, more preferably 1:0.08-0.2,ratio of the magnesium compound to the solvent is 1 mol:75˜400 ml,preferably 1 mol:150˜300 ml, more preferably 1 mol:200˜250 ml, ratio byweight of the magnesium compound (on a solid basis) to the porouscarrier is 1:0.1-20, preferably 1:0.5-10, more preferably 1:1-5, ratioby volume of the precipitating agent to the solvent is 1:0.2˜5,preferably 1:0.5˜2, more preferably 1:0.8˜1.5, and ratio by molar of themagnesium compound (based on Mg) to the chemical treating agent (basedon the Group IVB metal) is 1:0.01-1, preferably 1:0.01-0.50, morepreferably 1:0.10-0.30.

10. The process according to any of the aforesaid aspects, wherein theprecipitating agent is one or more selected from the group consisting ofan alkane, a cyclic alkane, a halogenated alkane and a halogenatedcyclic alkane, preferably one or more selected from the group consistingof pentane, hexane, heptane, octane, nonane, decane, cyclohexane,cyclopentane, cycloheptane, cyclodecane, cyclononane, dichloromethane,dichloro hexane, dichloro heptane, trichloro methane, trichloro ethane,trichloro butane, dibromo methane, dibromo ethane, dibromo heptane,tribromo methane, tribromo ethane, tribromo butane, chlorinatedcyclopentane, chlorinated cyclohexane, chlorinated cycloheptane,chlorinated cyclooctane, chlorinated cyclononane, chlorinatedcyclodecane, brominated cyclopentane, brominated cyclohexane, brominatedcycloheptane, brominated cyclooctane, brominated cyclononane andbrominated cyclodecane, more preferably one or more selected from thegroup consisting of hexane, heptane, decane and cyclohexane, mostpreferably hexane.

11. The process according to any of the aforesaid aspects, wherein theGroup IVB metal compound is one or more selected from the groupconsisting of a Group IVB metal halide, a Group IVB metal alkylate, aGroup IVB metal alkoxylate, a Group IVB metal alkyl halide, and a GroupIVB metal alkoxy halide, preferably one or more selected from the groupconsisting of a Group IVB metal halide, more preferably one or moreselected from the group consisting of TiCl₄, TiBr₄, ZrCl₄, ZrBr₄, HfCl₄and HfBr₄, more preferably one or more selected from the groupconsisting of TiCl₄ and ZrCl₄.

12. The process according to any of the aforesaid aspects, wherein thealuminoxane is one or more selected from the group consisting of methylaluminoxane, ethyl aluminoxane, isobutyl aluminoxane and n-butylaluminoxane, preferably one or more selected from the group consistingof methyl aluminoxane and isobutyl aluminoxane, and the alkylaluminum isone or more selected from the group consisting of trimethyl aluminum,triethyl aluminum, tripropyl aluminum, triisobutyl aluminum, tri-n-butylaluminum, triisoamyl aluminum, tri-n-amyl aluminum, trihexyl aluminum,tri-iso-hexyl aluminum, diethyl methyl aluminum and ethyl dimethylaluminum, more preferably one or more selected from the group consistingof trimethyl aluminum, triethyl aluminum, tripropyl aluminum andtriisobutyl aluminum, most preferably one or more selected from thegroup consisting of triethyl aluminum and triisobutyl aluminum.

13. The process according to any of the aforesaid aspects, wherein ratioby molar of the magnesium compound (based on Mg) to the assistantchemical treating agent (based on Al) is 1:0-1.0, preferably 1:0-0.5,more preferably 1:0.1-0.5.

14. A supported nonmetallocene catalyst, produced in line with theprocess according to any of the aspects 1 to 13.

15. An olefin homopolymerization/copolymerization process, wherein thesupported nonmetallocene catalyst according to the aspect 14 is used asthe main catalyst, in combination of one or more selected from the groupconsisting of an aluminoxane, an alkylaluminum, a halogenated alkylaluminum, a fluoroborane, an alkylboron and an alkylboron ammonium saltas the co-catalyst, for homopolymerization or copolymerization of theolefin.

16. An olefin homopolymerization/copolymerization process, comprisingthe steps of: producing a supported nonmetallocene catalyst in line withthe process according to any of the aspects 1 to 13; and using thesupported nonmetallocene catalyst as the main catalyst, in combinationof one or more selected from the group consisting of an aluminoxane, analkylaluminum, a halogenated alkyl aluminum, a fluoroborane, analkylboron and an alkylboron ammonium salt as the co-catalyst, forhomopolymerization or copolymerization of the olefin.

Effect of the Invention

According to the first and second embodiments of this invention, thefollowing effects can be obtained.

The process for producing the supported nonmetallocene catalystaccording to this invention is simple and feasible. It is easy, toadjust the load of the nonmetallocene complex, and it is possible for itto perform sufficiently in catalyzing olefin polymerization to obtain anolefin polymer product.

According to the process of this invention (concerning the firstembodiment), the catalyst has been produced by directly drying theslurry, and therefore it is easy to adjust the composition and amount ofthe essential materials in the catalyst.

According to the process of this invention (concerning the secondembodiment), the catalyst has been produced by sufficientlyprecipitating the slurry in the presence of a precipitating agent andthen filtering, washing and drying same, and therefore the bondingbetween the essential materials in the catalyst is relatively strong.

When a catalyst system is constituted by using the catalyst according tothis invention in combination with a co-catalyst, the polymer resultedfrom olefin polymerization exhibits a narrowed molecular weightdistribution, when used for copolymerization, the catalyst system showsa significant co-monomer effect, i.e. under relatively the sameconditions, the activity in copolymerization is higher than that inhomopolymerization.

According to the third and fourth embodiments of this invention, thefollowing effects can be obtained.

The process for producing the supported nonmetallocene catalystaccording to this invention is simple and feasible, and it is easy tocontrol the composition and amount of the essential materials in thecatalyst. Further, it is easy to adjust the load of the nonmetallocenecomplex, and it is possible for it to perform sufficiently in catalyzingolefin polymerization to obtain an olefin polymer product. Stillfurther, it is possible to adjust the molecular weight distribution andthe viscosity averaged molecular weight of the polymer product (forexample, the ultra high molecular weight polyethylene) by altering theamount of the nonmetallocene complex to be introduced.

Further, by altering the amount of the assistant chemical treating agentand that of the chemical treating agent to be introduced, it is possibleto obtain a supported nonmetallocene catalyst showing a easilycontrollable polymerization activity, from low to high, wherebyresponding to different olefin polymerization requirements, and it ispossible to adjust the performances of the catalyst and that of thepolymer in combination of the step of altering the amount of thenonmetallocene complex to be introduced.

According to the process of this invention (concerning the fourthembodiment), the composite carrier has been produced by sufficientlyprecipitating the slurry in the presence of a precipitating agent andthen filtering, washing and drying same, and therefore the bondingbetween the essential materials in the catalyst is relatively strong.

The active components (i.e. the nonmetallocene complex and the chemicaltreating agent) in the supported nonmetallocene catalyst produced inline with the process according to this invention show a synergiceffect, i.e. the activity obtained with the case when both componentsexist is higher than that when only either component exists.

Further discovered is that, when a catalyst system is constituted byusing the catalyst according to this invention in combination with aco-catalyst, only a comparatively small amount of the co-catalyst (forexample, methyl aluminoxane or triethyl aluminium) is needed to achievea comparatively high polymerization activity, and when used forcopolymerization, the catalyst system shows a significant co-monomereffect, i.e. under relatively the same conditions, the activity incopolymerization is higher than that in homopolymerization. Further, thepolymer (for example polyethylene) resulted from olefinhomopolymerization or copolymerization has a desirable polymermorphology and a high polymer bulk density.

DETAILED DESCRIPTION OF THE INVENTION

This invention will be described in details hereinafter with referenceto the following specific embodiments. However, it is known that theprotection scope of this invention should not be construed as limited tothese specific embodiments, but rather determined by the attachedclaims.

According to this invention, generally disclosed are the following firstto fourth embodiments.

The first embodiment relates to a process for producing a supportednonmetallocene catalyst, which comprises the steps of: dissolving amagnesium compound and a nonmetallocene complex in a solvent, to obtaina magnesium compound solution; mixing a porous carrier or a thermallyactivated porous carrier with the magnesium compound solution to obtaina slurry; and drying the slurry to obtain the supported nonmetallocenecatalyst.

The second embodiment relates to a process for producing a supportednonmetallocene catalyst, which comprises the steps of: dissolving amagnesium compound and a nonmetallocene complex in a solvent, to obtaina magnesium compound solution; mixing a porous carrier or a thermallyactivated porous carrier with the magnesium compound solution to obtaina slurry; and introducing into the slurry a precipitating agent toobtain the supported nonmetallocene catalyst.

The third embodiment relates to a process for producing a supportednonmetallocene catalyst, which comprises the steps of: dissolving amagnesium compound and a nonmetallocene complex in a solvent, to obtaina magnesium compound solution; mixing a porous carrier or a thermallyactivated porous carrier with the magnesium compound solution to obtaina slurry; drying the slurry to obtain a composite carrier; and treatingthe composite carrier with a chemical treating agent selected from thegroup consisting of Group IVB metal compounds to obtain the supportednonmetallocene catalyst.

The fourth embodiment relates to a process for producing a supportednonmetallocene catalyst, which comprises the steps of: dissolving amagnesium compound and a nonmetallocene complex in a solvent, to obtaina magnesium compound solution; mixing a porous carrier or a thermallyactivated porous carrier with the magnesium compound solution to obtaina slurry; introducing into the slurry a precipitating agent to obtain acomposite carrier; and treating the composite carrier with a chemicaltreating agent selected from the group consisting of Group IVB metalcompounds to obtain the supported nonmetallocene catalyst.

First of all, the step of obtaining the magnesium compound solutionaccording to the first to fourth embodiments of this invention isdetailedly described as follows.

Specifically, the magnesium compound (solid) and the nonmetallocenecomplex are dissolved in a suitable solvent (hereinafter referred to asa solvent for dissolving the magnesium compound) to obtain the magnesiumcompound solution.

As the solvent, a C₆₋₁₂ aromatic hydrocarbon, a halogenated C₆₋₁₂aromatic hydrocarbon, an ester and an ether can be exemplified.Specifically, toluene, xylene, trimethyl benzene, ethyl benzene, diethylbenzene, chlorinated toluene, chlorinated ethyl benzene, brominatedtoluene, brominated ethyl benzene, ethyl acetate and tetrahydrofuran canbe exemplified. Preference is given to the C₆₋₁₂ aromatic hydrocarbon ortetrahydrofuran, more preferably tetrahydrofuran.

The solvents could be used with one kind or as a mixture of two or morekinds at any ratio therebetween.

For preparation of the magnesium compound solution, the magnesiumcompound and the nonmetallocene complex are metered into and dissolvedin said solvent.

During preparation of the magnesium compound solution, it is desirablethat the ratio of the magnesium compound (based on Mg and on a solidbasis) to the solvent for dissolving the magnesium compound is generally1 mol:75˜400 ml, preferably 1 mol:150˜300 ml, more preferably 1mol:200˜250 ml.

According to this invention, as the amount of the nonmetallocene complexto be used, it is desirable that the ratio by molar of the magnesiumcompound (based on Mg and on a solid basis) to the nonmetallocenecomplex is 1:0.01-1, preferably 1:0.04-0.4, more preferably 1:0.08-0.2.

The duration for preparing the magnesium compound solution (i.e. theduration for dissolving the magnesium compound and the nonmetallocenecomplex) is not specifically limited, usually 0.5 to 24 hours,preferably 4 to 24 hours. During preparation of the magnesium compoundsolution, any stirring means for example, a stirring paddle (whoserotational speed could be 10 to 1000 r/min), could be used to facilitatedissolution of the magnesium compound and the nonmetallocene complex. Ifneeded, heat can be suitably applied to facilitate the dissolution.

The magnesium compound is further described as follows.

According to this invention, the term “magnesium compound” is explainedin a normal sense as known in this field, and refers to an organic orinorganic solid anhydrous Mg-containing compound conventionally used asa carrier for a supported catalyst for olefin polymerization.

According to this invention, as the magnesium compound, a magnesiumhalide, an alkoxy magnesium halide, an alkoxy magnesium, an alkylmagnesium, an alkyl magnesium halide and an alkyl alkoxy magnesium canbe exemplified.

Specifically, the magnesium halide for example, could be selected fromthe group consisting of magnesium chloride (MgCl₂), magnesium bromide(MgBr₂), magnesium iodide (MgI₂) and magnesium fluoride (MgF₂), etc.,such as magnesium chloride.

The alkoxy magnesium halide for example, could be selected from thegroup consisting of methoxy magnesium chloride (Mg(OCH₃)Cl), ethoxymagnesium chloride (Mg(OC₂H₅)Cl), propoxy magnesium chloride(Mg(OC₃H₇)Cl), n-butoxy magnesium chloride (Mg(OC₄H₉)Cl), isobutoxymagnesium chloride (Mg(i-OC₄H₉)Cl), methoxy magnesium bromide(Mg(OCH₃)Br), ethoxy magnesium bromide (Mg(OC₂H₅)Br), propoxy magnesiumbromide (Mg(OC₃H₇)Br), n-butoxy magnesium bromide (Mg(OC₄H₉)Br),isobutoxy magnesium bromide (Mg(i-OC₄H₉)Br), methoxy magnesium iodide(Mg(OCH₃)I), ethoxy magnesium iodide (Mg(OC₂H₅)I), propoxy magnesiumiodide (Mg(OC₃H₇)I), n-butoxy magnesium iodide (Mg(OC₄H₉)I) andisobutoxy magnesium iodide (Mg(i-OC₄H₉)I), etc., such as methoxymagnesium chloride, ethoxy magnesium chloride and isobutoxy magnesiumchloride.

The alkoxy magnesium for example, could be selected from the groupconsisting of methoxy magnesium (Mg(OCH₃)₂), ethoxy magnesium(Mg(OC₂H₅)₂), propoxy magnesium (Mg(OC₃H₇)₂), butoxy magnesium(Mg(OC₄H₉)₂), isobutoxy magnesium (Mg(i-OC₄H₉)₂) and 2-ethyl hexyloxymagnesium (Mg(OCH₂CH(C₂H₅)C₄H)₂), etc., such as ethoxy magnesium andisobutoxy magnesium.

The alkyl magnesium for example, could be selected from the groupconsisting of methyl magnesium (Mg(CH₃)₂), ethyl magnesium (Mg(C₂H₅)₂),propyl magnesium (Mg(C₃H₇)₂), n-butyl magnesium (Mg(C₄H₉)₂) and isobutylmagnesium (Mg(i-C₄H₉)₂), etc., such as ethyl magnesium and n-butylmagnesium.

The alkyl magnesium halide for example, could be selected from the groupconsisting of methyl magnesium chloride (Mg(CH₃)Cl), ethyl magnesiumchloride (Mg(C₂H₅)Cl), propyl magnesium chloride (Mg(C₃H₇)Cl), n-butylmagnesium chloride (Mg(C₄H₉)Cl), isobutyl magnesium chloride(Mg(i-C₄H₉)Cl), methyl magnesium bromide (Mg(CH₃)Br), ethyl magnesiumbromide (Mg(C₂H₅)Br), propyl magnesium bromide (Mg(C₃H₇)Br), n-butylmagnesium bromide (Mg(C₄H₉)Br), isobutyl magnesium bromide(Mg(i-C₄H₉)Br), methyl magnesium iodide (Mg(CH₃)I), ethyl magnesiumiodide (Mg(C₂H₅)I), propyl magnesium iodide (Mg(C₃H₇)I), n-butylmagnesium iodide (Mg(C₄H₉)I) and isobutyl magnesium iodide(Mg(i-C₄H₉)I), etc., such as methyl magnesium chloride, ethyl magnesiumchloride and isobutyl magnesium chloride.

The alkyl alkoxy magnesium for example, could be selected from the groupconsisting of methyl methoxy magnesium (Mg(OCH₃)(CH₃)), methyl ethoxymagnesium (Mg(OC₂H₅)(CH₃)), methyl propoxy magnesium (Mg(OC₃H₇)(CH₃)),methyl n-butoxy magnesium (Mg(OC₄H₉)(CH₃)), methyl isobutoxy magnesium(Mg(i-OC₄H₉)(CH₃)), ethyl methoxy magnesium (Mg(OCH₃)(C₂H₅)), ethylethoxy magnesium (Mg(OC₂H₅)(C₂H₅)), ethyl propoxy magnesium(Mg(OC₃H₇)(C₂H₅)), ethyl n-butoxy magnesium (Mg(OC₄H₉)(C₂H₅)), ethylisobutoxy magnesium (Mg(i-OC₄H₉)(C₂H₅)), propyl methoxy magnesium(Mg(OCH₃)(C₃H₇)), propyl ethoxy magnesium (Mg(OC₂H₅)(C₃H₇)), propylpropoxy magnesium (Mg(OC₃H₇)(C₃H₇)), propyl n-butoxy magnesium(Mg(OC₄H₉)(C₃H₇)), propyl isobutoxy magnesium (Mg(i-OC₄H₉)(C₃H₇)),n-butyl methoxy magnesium (Mg(OCH₃)(C₄H₉)), n-butyl ethoxy magnesium(Mg(OC₂H₅)(C₄H₉)), n-butyl propoxy magnesium (Mg(OC₃H₇)(C₄H₉)), n-butyln-butoxy magnesium (Mg(OC₄H₉)(C₄H₉)), n-butyl isobutoxy magnesium(Mg(i-OC₄H₉)(C₄H₉)), isobutyl methoxy magnesium (Mg(OCH₃)(i-C₄H₉)),isobutyl ethoxy magnesium (Mg(OC₂H₅)(i-C₄H₉)), isobutyl propoxymagnesium (Mg(OC₃H₇)(i-C₄H₉)), isobutyl n-butoxy magnesium(Mg(OC₄H₉)(i-C₄H₉)) and isobutyl isobutoxy magnesium(Mg(i-OC₄H₉)(i-C₄H₉)), etc., such as butyl ethoxy magnesium.

The magnesium compounds could be used with one kind or as a mixture oftwo or more kinds, but without any limitation thereto.

For example, if more than one magnesium compounds are used as a mixture,the ratio by molar of one magnesium compound to another magnesiumcompound in the mixture could be, for example, 0.25 to 4:1, such as 0.5to 3:1, such as 1 to 2:1.

According to this invention, the term “nonmetallocene complex” refers toan organic metallic compound capable of exhibiting a catalysis activityin olefin polymerization when combined with an aluminoxane (sometimeshereinafter referred to as a nonmetallocene complex for olefinpolymerization). The compound contains a central metal atom and at leastone multi-dentate ligand (preferably a tri or more-dentate ligand)bonding to the central metal atom by a coordination bond. The term“nonmetallocene ligand” corresponds to the multi-dentate ligand.

According to this invention, the nonmetallocene complex is selected fromthe compounds having the following structure,

According to aforesaid chemical formula, the ligands which form acoordination bond with the central metal atom M contain n of the groupsX and m of the multi-dentate ligands (the structure in the parenthesis).According to the chemical formula of said multi-dentate ligand, thegroups A, D and E (the coordination groups) form a coordination bondwith the central metal atom M through the coordination atoms (forexample, hetero atoms like N, O, S, Se and P) contained in these groups.

According to this invention, the absolute value of the total sum of thenegative charges carried by all of the ligands (including the group Xand the multi-dentate ligand) is equal to that of the positive chargescarried by the central metal atom M.

According to a further embodiment of this invention, the nonmetallocenecomplex is selected from the following compound (A) and the followingcompound (B),

According to a further embodiment of this invention, the nonmetallocenecomplex is selected from the following compound (A-1), the followingcompound (A-2), the following compound (A-3), the following compound(A-4), the following compound (B-1), the following compound (B-2), thefollowing compound (B-3), and the following compound (B-4),

In all of the aforesaid formulae,

q is 0 or 1;

d is 0 or 1;

m is 1, 2 or 3;

M is selected from the group consisting of a Group III to XI metal atomin the Periodic Table of Elements, preferably a Group IVB metal atom,for example, Ti(IV), Zr(IV), Hf(IV), Cr(III), Fe(III), Ni(II), Pd(II) orCo(II);

n is 1, 2, 3 or 4, depending on the valence of the central metal atom M;

X is selected from the group consisting of a halogen atom, a hydrogenatom, a C₁-C₃₀ hydrocarbyl, a substituted C₁-C₃₀ hydrocarbyl, anoxygen-containing group, a nitrogen-containing group, asulfur-containing group, a boron-containing group, analuminium-containing group, a phosphor-containing group, asilicon-containing group, a germanium-containing group, and atin-containing group, when multiple Xs exist, the Xs may be the same asor different from one another, and may form a bond or a ring with oneanother;

A is selected from the group consisting of an oxygen atom, a sulfuratom, a selenium atom,

—NR²³R²⁴, —N(O)R²⁵R²⁶,

—PR²⁸R²⁹, —P(O)R³⁰OR³¹, a sulfone group, a sulfoxide group and—Se(O)R³⁹, wherein N, O, S, Se and P each represents a coordinationatom;

B is selected from the group consisting of a nitrogen atom, anitrogen-containing group, a phosphor-containing group and a C₁-C₃₀hydrocarbyl;

D is selected from the group consisting of a nitrogen atom, an oxygenatom, a sulfur atom, a selenium atom, a phosphor atom, anitrogen-containing group, a phosphor-containing group, a C₁-C₃₀hydrocarbyl, a sulfone group, a sulfoxide group,

—N(O)R²⁵R²⁶,

and —P(O)R³²(OR³³), wherein N, O, S, Se and P each represents acoordination atom;

E is selected from the group consisting of a nitrogen-containing group,an oxygen-containing group, a sulfur-containing group, aselenium-containing group, a phosphor-containing group and a cyano group(—CN), wherein N, O, S, Se and P each represents a coordination atom;

F is selected from the group consisting of a nitrogen atom, anitrogen-containing group, an oxygen-containing group, asulfur-containing group, a selenium-containing group and aphosphor-containing group, wherein N, O, S, Se and P each represents acoordination atom;

G is selected from the group consisting of a C₁-C₃₀ hydrocarbyl, asubstituted C₁-C₃₀ hydrocarbyl and an inert functional group;

Y is selected from the group consisting of an oxygen atom, anitrogen-containing group, an oxygen-containing group, asulfur-containing group, a selenium-containing group and aphosphor-containing group, wherein N, O, S, Se and P each represents acoordination atom;

Z is selected from the group consisting of a nitrogen-containing group,an oxygen-containing group, a sulfur-containing group, aselenium-containing group, a phosphor-containing group and a cyano group(—CN), for example, —NR²³R²⁴, —N(O)R²⁵R²⁶, —PR²⁸R²⁹, —P(O)R³⁰R³¹, —OR³⁴,—SR³⁵, —S(O)R³⁶, —SeR³⁸ or —Se(O)R³⁹, wherein N, O, S, Se and P eachrepresents a coordination atom;

→ represents a single bond or a double bond;

- represents a covalent bond or an ionic bond;

--- represents a coordination bond, a covalent bond or an ionic bond;

R¹ to R⁴, R⁶ to R³⁶, R³⁸ and R³⁹ are each independently selected fromthe group consisting of a hydrogen atom, a C₁-C₃₀ hydrocarbyl, asubstituted C₁-C₃₀ hydrocarbyl (preferably a halogenated hydrocarbyl,for example —CH₂Cl and —CH₂CH₂Cl) and an inert functional group, whereinthese groups may be identical to or different from one another, and anyadjacent groups (for example R¹ and R², R⁶ and R⁷, R⁷ and R⁸, R⁸ and R⁹,R¹³ and R¹⁴, R¹⁴ and R¹⁵, R¹⁵ and R¹⁶, R¹⁸ and R¹⁹, R¹⁹ and R²⁰, R²⁰ andR²¹, R²³ and R²⁴, or R²⁵ and R²⁶) may form a bond or a ring (preferablyan aromatic ring, for example a unsubstituted benzene ring or a benzenering substituted by one to four of a C₁-C₃₀ hydrocarbyl, a substitutedC₁-C₃₀ hydrocarbyl (preferably a halogenated hydrocarbyl, for example—CH₂Cl and —CH₂CH₂Cl) or an inert functional group) with one another;and

R⁵ is selected from the group consisting of the lone pair electron onthe nitrogen atom, a hydrogen atom, a C₁-C₃₀ hydrocarbyl, a substitutedC₁-C₃₀ hydrocarbyl, an oxygen-containing group, a sulfur-containinggroup, a nitrogen-containing group, a selenium-containing group, and aphosphor-containing group, with the proviso that when R⁵ is theoxygen-containing group, the sulfur-containing group, thenitrogen-containing group, the selenium-containing group or thephosphor-containing group, N, O, S, P and Se in the group R⁵ each canact as a coordination atom to coordinate with the central metal atom(the Group IVB metal atom).

According to this invention, in all of the aforesaid formulae, ifnecessary, any two or more adjacent groups (for example R²¹ and thegroup Z, or R¹³ and the group Y) may form a ring with one another,preferably a C₆-C₃₀ aromatic heteroatomic ring containing the heteroatom originated from the group Z or Y, for example a pyridine ring,wherein the aromatic heteroatomic ring is optionally substituted by oneor more substituent(s) selected from the group consisting of a C₁-C₃₀hydrocarbyl, a substituted C₁-C₃₀ hydrocarbyl and an inert functionalgroup.

In the context of this invention, the halogen atom is selected from thegroup consisting of F, Cl, Br and I, the nitrogen-containing group isselected from the group consisting of

—NR²³R²⁴, -T-NR²³R²⁴ and —N(O)R²⁵R²⁶, the phosphor-containing group isselected from the group consisting of

—PR²⁸R²⁹, —P(O)R³⁰R³¹ and —P(O)R³²(OR³³), the oxygen-containing group isselected from the group consisting of hydroxy, —OR³⁴ and -T-OR³⁴, thesulfur-containing group is selected from the group consisting of —SR³⁵,-T-SR³⁵, —S(O)R³⁶ and -T-SO₂R³⁷, the selenium-containing group isselected from the group consisting of —SeR³⁸, -T-SeR³⁸, —Se(O)R³⁹ and-T-Se(O)R³⁹, the group T is selected from the group consisting of aC₁-C₃₀ hydrocarbyl, a substituted C₁-C₃₀ hydrocarbyl and an inertfunctional group, and R³⁷ is selected from the group consisting of ahydrogen atom, a C₁-C₃₀ hydrocarbyl, a substituted C₁-C₃₀ hydrocarbyland an inert functional group.

In the context of this invention, the C₁-C₃₀ hydrocarbyl is selectedfrom the group consisting of a C₁-C₃₀ alkyl group (for example a C₁-C₆alkyl group, for example isobutyl group), a C₇-C₅₀ alkylaryl group (forexample tolyl, xylyl, diisobutyl phenyl), a C₇-C₅₀ aralkyl group (forexample benzyl), a C₃-C₃₀ cyclic alkyl group, a C₂-C₃₀ alkenyl group, aC₂-C₃₀ alkynyl group, a C₆-C₃₀ aryl group (for example phenyl, naphthyl,anthracyl), a C₈-C₃₀ fused-ring group and a C₄-C₃₀ heterocyclic group,wherein the heterocyclic group contains 1 to 3 hetero atom(s) selectedfrom the group consisting of a nitrogen atom, an oxygen atom and asulfur atom, including for example a pyridyl group, a pyrrolyl group, afuranyl group and a thienyl group.

In the context of this invention, depending on the nature of therelevant groups to which the C₁-C₃₀ hydrocarbyl bond, it is obvious to aperson skilled in the art that the C₁-C₃₀ hydrocarbyl may intend aC₁-C₃₀ hydrocarbon-diyl (a bivalent group, or referred to as a C₁-C₃₀hydrocarbylene group) or a C₁-C₃₀ hydrocarbon-triyl (a trivalent group).

In the context of this invention, the substituted C₁-C₃₀ hydrocarbylintends the aforesaid C₁-C₃₀ hydrocarbyl having one or more inertsubstituent(s). By inert, it means that these inert substituents willnot substantially interfere with the coordination process between theaforesaid coordination groups (i.e. the aforesaid groups A, D, E, F, Yand Z, or further, if applicable, the group R⁵) and the central metalatom M. In other words, restricted by the specific chemical structure ofthe present multi-dentate ligand, these substituents are incapable of orhave no chance (due to for example steric hindrance) to coordinate withthe central metal atom M to form a coordination bond therewith.Generally, the inert substituent refers to the aforesaid halogen atom orC₁-C₃₀ alkyl group (for example a C₁-C₆ alkyl group, for exampleisobutyl group).

In the context of this invention, the term “inert functional group” doesnot comprise the aforesaid C₁-C₃₀ hydrocarbyl or substituted C₁-C₃₀hydrocarbyl in its concept. As the inert functional group, the halogenatom, the oxygen-containing group, the nitrogen-containing group, asilicon-containing group, a germanium-containing group, thesulfur-containing group, a tin-containing group, a C₁-C₁₀ ester group ora nitro group (—NO₂) can be exemplified.

In the context of this invention, restricted by the specific structureof the present multi-dentate ligand, the inert functional group ischaracterized that:

(1) it will not interfere with the coordination process between theaforesaid group A, D, E, F, Y or Z and the central metal atom M, and

(2) its capability to form a coordination bond with the central metalatom M is inferior to the capability of the aforesaid group A, D, E, F,Y or Z to form a coordination bond with the central metal atom M, andwill not displace the formed coordination between the central metal atomM and these groups.

In the context of this invention, the boron-containing group is selectedfrom the group consisting of BF₄ ⁻, (C₆F₅)₄B⁻ and (R⁴⁰BAr₃)⁻, thealuminium-containing group is selected from the group consisting of analkyl aluminium, AlPh₄ ⁻, AlF₄ ⁻, AlCl₄ ⁻, AlBr₄ ⁻, AlI₄ ⁻ and R⁴¹AlAr₃⁻, the silicon-containing group is selected from the group consisting of—SiR⁴²R⁴³R⁴⁴, and -T-SiR⁴⁵, the germanium-containing group is selectedfrom the group consisting of —GeR⁴⁶R⁴⁷R⁴⁸, and -T-GeR⁴⁹, thetin-containing group is selected from the group consisting of—SnR⁵⁰R⁵¹R⁵², -T-SnR⁵³ and -T-Sn(O)R⁵⁴, the Ar group represents a C₆-C₃₀aryl group, R⁴⁰ to R⁵⁴ are each independently selected from the groupconsisting of a hydrogen atom, the C₁-C₃₀ hydrocarbyl, the substitutedC₁-C₃₀ hydrocarbyl and the inert functional group, wherein these groupsmay be identical to or different from one another, and any adjacentgroups may form a bond or a ring with one another, and the group T isdefined as aforesaid.

As the nonmetallocene complex, the following compounds can be furtherexemplified.

As the nonmetallocene complex, the following compounds can be furtherexemplified.

As the nonmetallocene complex, the following compounds can be furtherexemplified.

As the nonmetallocene complex, the following compounds can be furtherexemplified.

The nonmetallocene complexes could be used with one kind or as a mixtureof two or more kinds at any ratio therebetween.

According to this invention, the multi-dentate ligand in thenonmetallocene complex does not correspond to or comprise the di-ethercompound conventionally used in this field as an electron donorcompound.

According to this invention, the multi-dentate ligand or thenonmetallocene complex can be produced in line with any process known inthis field by a person skilled in the art. For the details of theprocess, one can refer to for example WO03/010207 or the Chinese PatentNos. ZL01126323.7 and ZL02110844.7. All the references cited herein areincorporated by reference in their entireties.

According to the first to fourth embodiments of this invention, theporous carrier is mixed with the magnesium compound solution wherebyobtaining the slurry.

According to this invention, mixing of the porous carrier with themagnesium compound solution could be conducted by using any conventionalprocess, without any specific limitation. For example, the mixing couldbe conducted by for example at a temperature ranging from the normaltemperature to the temperature at which the magnesium compound solutionis prepared, metering the porous carrier into the magnesium compoundsolution, or metering the magnesium compound solution into the porouscarrier, and then mixing with each other for 0.1 to 8 hours, such as 0.5to 4 hours, such as 1 to 2 hours, if necessary, under stirring.

According to this invention, as the amount of the porous carrier to beused, it is desirable that the ratio by weight of the magnesium compound(based on the magnesium compound solid contained in the magnesiumcompound solution) to the porous carrier is 1:0.1-20, preferably1:0.5-10, more preferably 1:1-5.

The resultant slurry is a slurry system. Though it is not alwaysnecessary, it is preferably for the slurry to stand in a sealed statefor a determined duration after preparation, so as to secure uniformityof the system, wherein the duration could be 2 to 48 hours, such as 4 to24 hours, such as 6 to 18 hours.

The porous carrier is further described as follows.

According to this invention, as the porous carrier, the organic orinorganic porous solid conventionally used in this field as the carrierfor producing a supported catalyst can be exemplified.

Specifically, as the organic porous solid, olefin homopolymers orcopolymers, vinyl alcohol homopolymers or copolymers, cyclodextrins,polyesters or co-polyesters, polyamides or co-polyamides, vinyl chloridehomopolymers or copolymers, acrylic ester homopolymers or copolymers,methacrylic ester homopolymers or copolymers, styrene homopolymers orcopolymers, and partly crosslinked products of these homopolymers orcopolymers can be exemplified, preferably partly crosslinked styrenepolymers (for example one having a crosslinking degree of from 2% toless than 100%).

According to a further embodiment of this invention, the organic poroussolid has one or more active functional group(s) for example selectedfrom the group consisting of a hydroxyl group, a primary amino group, asecondary amino group, a sulfonic acid group, a carboxyl group, an amidogroup, a N-mono substituted amido group, a sulfonamido group, a N-monosubstituted sulfonamido group, a mercapto group, an imido group and ahydrazide group, on its surface, wherein the carboxyl group or thehydroxyl group is preferred.

According to a further embodiment of this invention, the organic poroussolid is subjected to a thermal activation before use. The thermalactivation can be conducted in a normal way. For example, the organicporous solid is treated by heat under a reduced pressure or under aninert gas atmosphere. By an inert gas atmosphere herein, it means thatthere exists no component capable of reacting with the organic poroussolid in the gas atmosphere, or if does exist, only at a rather minoramount. As the inert gas atmosphere, a nitrogen gas or rare gasatmosphere can be exemplified, preferably a nitrogen gas atmosphere. Inview of the poor heat resistance, the thermal activation in connectionwith the organic porous solid should be conducted with the proviso thatthe inherent structure and composition of the organic porous solid willnot be destroyed. Generally, the temperature at which the thermalactivation is conducted is from 50 to 400° C., preferably 100-250° C.,while the duration for the thermal activation is from 1 to 24 hours,preferably 2 to 12 hours. After thermal activation, the organic poroussolid should be stored under a positive pressure under an inert gasatmosphere before use.

As the inorganic porous solid, a refractory oxide of a Group IIA, IIIA,IVA or IVB metal in the Periodic Table of Elements (for example silica(also known as silicon dioxide or silica gel), alumina, magnesia,titania, zirconia, or thorium oxide), or a refractory composite oxide ofany of these metals (for example, silica-alumina, magnesia-alumina,titania-silica, titania-magnesia, or titania-alumina), and clay,molecular sieve (for example ZSM-5 or MCM-41), mica, montmorillonite,bentonite or kieselguhr can be exemplified. As the inorganic poroussolid, the oxide produced by high temperature hydrolysis of a gaseousmetal halide or a gaseous silicon compound, for example silica producedby high temperature hydrolysis of silicon tetrachloride, or aluminaproduced by high temperature hydrolysis of AlCl3 can be furtherexemplified.

As the inorganic porous solid, preference is given to silica, alumina,magnesia, silica-alumina, magnesia-alumina, titanic-silica, titaniumoxide, molecular sieve and montmorillonite, more preferably silica.

According to this invention, suitable silica can be produced by anyconventional process, or is any commercially available one. For example,Grace 955, Grace 948, Grace SP9-351, Grace SP9-485, Grace SP9-10046,Daysion Syloid 245 and Aerosil 812 from the Grace company, ES70, ES70X,ES70Y, ES70W, ES757, EP10X and EP11 from the Ineos company, or CS-2133and MS-3040 from the PQ company can be exemplified.

According to a further embodiment of this invention, the inorganicporous solid has an active functional group on its surface, for examplea hydroxyl group.

According to a further embodiment of this invention, the inorganicporous solid is subjected to a thermal activation before use. Thethermal activation can be conducted in a normal way. For example, theinorganic porous solid is treated by heat under a reduced pressure orunder an inert gas atmosphere. By an inert gas atmosphere herein, itmeans that there exists no component capable of reacting with theinorganic porous solid in the gas atmosphere, or if does exist, only ata rather minor amount. As the inert gas atmosphere, a nitrogen gas orrare gas atmosphere can be exemplified, preferably a nitrogen gasatmosphere. Generally, the temperature at which the thermal activationis conducted is from 200 to 800° C., preferably 400-700° C., preferably400-650° C., while the duration for the thermal activation is from 0.5to 24 hours, preferably 2 to 12 hours, preferably 4 to 8 hours. Afterthermal activation, the inorganic porous solid should be stored under apositive pressure under an inert gas atmosphere before use.

According to this invention, the surface area (measured by the BETmethod) of the porous carrier is generally, but not limiting to, 10 to1000 m²/g, or 100 to 600 m²/g. The pore volume (measured by the nitrogenadsorption method) of the porous carrier is generally 0.1 to 4 cm³/g, or0.2 to 2 cm³/g. The average particle size (measured by a laser particlesize analyzer) of the porous carrier is generally 1 to 500 μm, or 1 to100 μm.

According to this invention, the porous carrier can present in any form,for example, fine powder, particulate, sphere, aggregate, or other form.

According to the first embodiment of this invention, by directly dryingthe slurry, or by filtering, washing and drying the slurry, preferablydirectly drying, a freely flowable solid product can be obtained, whichcorresponds to the supported nonmetallocene catalyst of this invention.

According to the first embodiment of this invention, in the case ofdirectly drying the slurry, any conventional process, for example,drying under an inert gas atmosphere, vacuum drying or vacuum dryingunder heat, can be used, preferably vacuum drying under heat. The dryingis generally conducted at a temperature 5 to 15° C. lower than theboiling point of any solvent in the slurry, which would be a temperatureof 30 to 160° C. or 60 to 130° C., while the duration for the drying isgenerally, not limiting to, 2 to 24 hours.

According to the first embodiment of this invention, in case offiltering, washing and drying of the slurry, there is no limitation tothe process for filtering, washing or drying, and any conventionalprocess conventionally used in this field can be used as needed.According to this invention, the washing can be generally conducted for1 to 6 times, preferable 2 to 3 times. Herein, the solvent for washingcan be the same as or different from that contained in the slurry. Thedrying can be conducted in a conventional way, preferably as describedin connection with the case of directly drying the slurry.

Further, according to the second embodiment of this invention, bymetering into the slurry a precipitating agent, solid matter (solidproduct) is precipitated out of the slurry, whereby obtaining thesupported nonmetallocene catalyst of this invention.

Or, according to the fourth embodiment of this invention, by meteringinto the slurry a precipitating agent, solid matter (solid product) isprecipitated out of the slurry, whereby obtaining the composite carrier.

The precipitating agent is further described as follows.

According to this invention, the term “precipitating agent” is explainedin a normal sense as known in this field, and refers to a chemicallyinert liquid capable of lowering the solubility of a solute (for examplethe magnesium compound) in its solution to the degree that said soluteprecipitates from the solution as solid matter.

According to this invention, as the precipitating agent, a solvent thatrepresents as a poor solvent for the magnesium compound while as a goodsolvent for the solvent for dissolving the magnesium compound can beexemplified. For example, an alkane, a cyclic alkane, a halogenatedalkane and a halogenated cyclic alkane can be further exemplified.

As the alkane, exemplified is pentane, hexane, heptane, octane, nonaneand decane, and the like, such as hexane, heptane and decane, such ashexane.

As the cyclic alkane, exemplified is cyclohexane, cyclo pentane, cycloheptane, cyclo decane, cyclo nonane, and the like, such as cyclo hexane.

As the halogenated alkane, exemplified is dichloro methane, dichlorohexane, dichloro heptane, trichloro methane, trichloro ethane, trichlorobutane, dibromo methane, dibromo ethane, dibromo heptane, tribromomethane, tribromo ethane, tribromo butane, and the like.

As the halogenated cyclic alkane, exemplified is chlorinated cyclopentane, chlorinated cyclo hexane, chlorinated cyclo heptane,chlorinated cyclo octane, chlorinated cyclo nonane, chlorinated cyclodecane, brominated cyclo pentane, brominated cyclo hexane, brominatedcyclo heptane, brominated cyclo octane, brominated cyclo nonane,brominated cyclo decane, and the like.

The precipitating agent can be used with one kind or as a mixture of twoor more kinds at any ratio therebetween.

The precipitating agent could be added all at once or dropwise, such asall at once. During the precipitation, any stirring means could be usedto facilitate uniform dispersion of the precipitating agent throughoutthe slurry, and eventually facilitate precipitation of the solidproduct. The stirring means could be in any form, for example, as astirring paddle, whose rotational speed could be 10 to 1000 r/min.

There is no limitation as to the amount of the precipitating agent to beused, generally, the ratio by volume of the precipitating agent to thesolvent for dissolving the magnesium compound is 1:0.2˜5, preferably1:0.5˜2, more preferably 1:0.8˜1.5.

There is no limitation as to the temperature at which the precipitatingagent is, such as the normal temperature. Further, the precipitationprocess can be generally conducted at the normal temperature as well.

After completely precipitated, the thus obtained solid product isfiltered, washed and dried. There is no limitation to the process forfiltering, washing or drying, and any conventional processconventionally used in this field can be used as needed.

If needed, the washing can be generally conducted for 1 to 6 times,preferable 2 to 3 times. Herein, the solvent for washing can be the sameas or different from the precipitating agent.

The drying can be conducted in line with a conventional process, forexample, drying under an inert gas atmosphere, vacuum drying or vacuumdrying under heat, preferably drying under an inert gas atmosphere orvacuum drying under heat, most preferably vacuum drying under heat.

The drying is generally conducted at a temperature ranging from thenormal temperature to 100° C. for a duration by which the mass in dryingwill not loss weight any further. For example, in the case whereintetrahydrofuran is used as the solvent for dissolving the magnesiumcompound, the drying is generally conducted at about 80° C. under vacuumfor a duration of 2 to 12 hours, while toluene is used as the solventfor dissolving the magnesium compound, the drying is generally conductedat about 100° C. under vacuum for a duration of 4 to 24 hours.

Further, according to the third embodiment of this invention, bydirectly drying the slurry, or by filtering, washing and drying theslurry, preferably directly drying, a freely flowable solid product canbe obtained, which corresponds to the composite carrier of thisinvention.

According to the third embodiment of this invention, in the case ofdirectly drying the slurry, any conventional process, for example,drying under an inert gas atmosphere, vacuum drying or vacuum dryingunder heat, can be used, preferably vacuum drying under heat. The dryingis generally conducted at a temperature 5 to 15° C. lower than theboiling point of any solvent in the slurry, while the duration for thedrying is generally, not limiting to, 2 to 24 hours.

According to the third embodiment of this invention, in case offiltering, washing and drying of the slurry, there is no limitation tothe process for filtering, washing or drying, and any conventionalprocess conventionally used in this field can be used as needed. Ifneeded, the washing can be generally conducted for 1 to 6 times,preferable 2 to 3 times. Herein, the solvent for washing can be the sameas or different from that contained in the slurry. The drying can beconducted in a conventional way, preferably as described in connectionwith the case of directly drying the slurry.

Then, according to the third and fourth embodiments of this invention,the composite carrier is treated with a chemical treating agent selectedfrom the group consisting of Group IVB metal compounds (referred to asthe chemical treating step hereinafter) so as to obtain the supportednonmetallocene catalyst of this invention.

The chemical treating agent is further described as follows.

According to this invention, a Group IVB metal compound is used as thechemical treating agent.

As the Group IVB metal compound, exemplified is a Group IVB metalhalide, a Group IVB metal alkylate, a Group IVB metal alkoxylate, aGroup IVB metal alkyl halide, and a Group IVB metal alkoxy halide.

As the Group IVB metal halide, the Group IVB metal alkylate, the GroupIVB metal alkoxylate, the Group IVB metal alkyl halide and the Group IVBmetal alkoxy halide, exemplified is a compound having the followinggeneral formula (IV).M(OR¹)_(m)X_(n)R² _(4-m-n)  (IV)wherein,

m is 0, 1, 2, 3, or 4,

n is 0, 1, 2, 3, or 4,

M is a Group IVB metal in the Periodic Table of Elements, for example,titanium, zirconium, hafnium and the like,

X is a halogen atom, for example, F, Cl, Br, and I, and

R¹ and R² each independently is selected from the group consisting of aC₁-C₁₀ alkyl, for example, methyl, ethyl, propyl, n-butyl, isobutyl andthe like, R¹ and R² could be identical to or different from each other.

Specifically, the Group IVB metal halide could be exemplified as forexample, titanium tetrafluoride (TiF₄), titanium tetrachloride (TiCl₄),titanium tetrabromide (TiBr₄), titanium tetraiodide (TiI₄), zirconiumtetrafluoride (ZrF₄), zirconium tetrachloride (ZrCl₄), zirconiumtetrabromide (ZrBr₄), zirconium tetraiodide (ZrI₄), hafniumtetrafluoride (HfF₄), hafnium tetrachloride (HfCl₄), hafniumtetrabromide (HfBr₄), hafnium tetraiodide (HfI₄).

As the Group IVB metal alkylate, exemplified is tetramethyl titanium(Ti(CH₃)₄), tetraethyl titanium (Ti(CH₃CH₂)₄), tetraisobutyl titanium(Ti(i-C₄H₉)₄), tetran-butyl titanium (Ti(C₄H₉)₄), triethyl methyltitanium (Ti(CH₃)(CH₃CH₂)₃), diethyl dimethyl titanium(Ti(CH₃)₂(CH₃CH₂)₂), trimethyl ethyl titanium (Ti(CH₃)₃(CH₃CH₂)),triisobutyl methyl titanium (Ti(CH₃)(i-C₄H₉)₃), diisobutyl dimethyltitanium (Ti(CH₃)₂(i-C₄H₉)₂), trimethyl isobutyl titanium(Ti(CH₃)₃(i-C₄H₉)), triisobutyl ethyl titanium (Ti(CH₃CH₂)(i-C₄H₉)₃),diisobutyl diethyl titanium (Ti(CH₃CH₂)₂(i-C₄H₉)₂), triethyl isobutyltitanium (Ti(CH₃CH₂)₃(i-C₄H₉)), trin-butyl methyl titanium(Ti(CH₃)(C₄H₉)₃), din-butyl dimethyl titanium (Ti(CH₃)₂(C₄H₉)₂),trimethyl n-butyl titanium (Ti(CH₃)₃(C₄H₉)), trin-butyl methyl titanium(Ti(CH₃CH₂)(C₄H₉)₃), din-butyl diethyl titanium (Ti(CH₃CH₂)₂(C₄H₉)₂),triethyl n-butyl titanium (Ti(CH₃CH₂)₃(C₄H₉)), and so on,

tetramethyl zirconium (Zr(CH₃)₄), tetraethyl zirconium (Zr(CH₃CH₂)₄),tetraisobutyl zirconium (Zr(i-C₄H₉)₄), tetran-butyl zirconium(Zr(C₄H₉)₄), triethyl methyl zirconium (Zr(CH₃)(CH₃CH₂)₃), diethyldimethyl zirconium (Zr(CH₃)₂(CH₃CH₂)₂), trimethyl ethyl zirconium(Zr(CH₃)₃(CH₃CH₂)), triisobutyl methyl zirconium (Zr(CH₃)(i-C₄H₉)₃),diisobutyl dimethyl zirconium (Zr(CH₃)₂(i-C₄H₉)₂), trimethyl isobutylzirconium (Zr(CH₃)₃(i-C₄H₉)), triisobutyl ethyl zirconium(Zr(CH₃CH₂)(i-C₄H₉)₃), diisobutyl diethyl zirconium(Zr(CH₃CH₂)₂(i-C₄H₉)₂), triethyl isobutyl zirconium(Zr(CH₃CH₂)₃(i-C₄H₉)), trin-butyl methyl zirconium (Zr(CH₃)(C₄H₉)₃),din-butyl dimethyl zirconium (Zr(CH₃)₂(C₄H₉)₂), trimethyl n-butylzirconium (Zr(CH₃)₃(C₄H₉)), trin-butyl methyl zirconium(Zr(CH₃CH₂)(C₄H₉)₃), din-butyl diethyl zirconium (Zr(CH₃CH₂)₂(C₄H₉)₂),triethyl n-butyl zirconium (Zr(CH₃CH₂)₃(C₄H₉)), and so on,

tetramethyl hafnium (Hf(CH₃)₄), tetraethyl hafnium (Hf(CH₃CH₂)₄),tetraisobutyl hafnium (Hf(i-C₄H₉)₄), tetran-butyl hafnium (Hf(C₄H₉)₄),triethyl methyl hafnium (Hf(CH₃)(CH₃CH₂)₃), diethyl dimethyl hafnium(Hf(CH₃)₂(CH₃CH₂)₂), trimethyl ethyl hafnium (Hf(CH₃)₃(CH₃CH₂)),triisobutyl methyl hafnium (Hf(CH₃)(i-C₄H₉)₃), diisobutyl dimethylhafnium (Hf(CH₃)₂(i-C₄H₉)₂), trimethyl isobutyl hafnium(Hf(CH₃)₃(i-C₄H₉)), triisobutyl ethyl hafnium (Hf(CH₃CH₂)(i-C₄H₉)₃),diisobutyl diethyl hafnium (Hf(CH₃CH₂)₂(i-C₄H₉)₂), triethyl isobutylhafnium (Hf(CH₃CH₂)₃(i-C₄H₉)), trin-butyl methyl hafnium(Hf(CH₃)(C₄H₉)₃), din-butyl dimethyl hafnium (Hf(CH₃)₂(C₄H₉)₂),trimethyl n-butyl hafnium (Hf(CH₃)₃(C₄H₉)), trin-butyl methyl hafnium(Hf(CH₃CH₂)(C₄H₉)₃), din-butyl diethyl hafnium (Hf(CH₃CH₂)₂(C₄H₉)₂),triethyl n-butyl hafnium (Hf(CH₃CH₂)₃(C₄H₉)), and so on.

As the Group IVB metal alkoxylate, exemplified is tetramethoxy titanium(Ti(OCH₃)₄), tetraethoxy titanium (Ti(OCH₃CH₂)₄), tetraisobutoxytitanium (Ti(i-OC₄H₉)₄), tetran-butoxy titanium (Ti(OC₄H₉)₄), triethoxymethoxy titanium (Ti(OCH₃)(OCH₃CH₂)₃), diethoxy dimethoxy titanium(Ti(OCH₃)₂(OCH₃CH₂)₂), trimethoxy ethoxy titanium (Ti(OCH₃)₃(OCH₃CH₂)),triisobutoxy methoxy titanium (Ti(OCH₃)(i-OC₄H₉)₃), diisobutoxydimethoxy titanium (Ti(OCH₃)₂(i-OC₄H₉)₂), trimethoxy isobutoxy titanium(Ti(OCH₃)₃(i-OC₄H₉)), triisobutoxy ethoxy titanium(Ti(OCH₃CH₂)(i-OC₄H₉)₃), diisobutoxy diethoxy titanium(Ti(OCH₃CH₂)₂(i-OC₄H₉)₂), triethoxy isobutoxy titanium(Ti(OCH₃CH₂)₃(i-OC₄H₉)), tri-n-butoxy methoxy titanium(Ti(OCH₃)(OC₄H₉)₃), din-butoxy dimethoxy titanium (Ti(OCH₃)₂(OC₄H₉)₂),trimethoxy n-butoxy titanium (Ti(OCH₃)₃(OC₄H₉)), tri-n-butoxy methoxytitanium (Ti(OCH₃CH₂)(OC₄H₉)₃), din-butoxy diethoxy titanium(Ti(OCH₃CH₂)₂(OC₄H₉)₂), triethoxy n-butoxy titanium(Ti(OCH₃CH₂)₃(OC₄H₉)), and so on,

tetramethoxy zirconium (Zr(OCH₃)₄), tetraethoxy zirconium(Zr(OCH₃CH₂)₄), tetraisobutoxy zirconium (Zr(i-OC₄H₉)₄), tetran-butoxyzirconium (Zr(OC₄H₉)₄), triethoxy methoxy zirconium(Zr(OCH₃)(OCH₃CH₂)₃), diethoxy dimethoxy zirconium(Zr(OCH₃)₂(OCH₃CH₂)₂), trimethoxy ethoxy zirconium (Zr(OCH₃)₃(OCH₃CH₂)),triisobutoxy methoxy zirconium (Zr(OCH₃)(i-OC₄H₉)₃), diisobutoxydimethoxy zirconium (Zr(OCH₃)₂(i-OC₄H₉)₂), trimethoxy isobutoxyzirconium (Zr(OCH₃)₃(i-C₄H₉)), triisobutoxy ethoxy zirconium(Zr(OCH₃CH₂)(i-OC₄H₉)₃), diisobutoxy diethoxy zirconium(Zr(OCH₃CH₂)₂(i-OC₄H₉)₂), triethoxy isobutoxy zirconium(Zr(OCH₃CH₂)₃(i-OC₄H₉)), tri-n-butoxy methoxy zirconium(Zr(OCH₃)(OC₄H₉)₃), din-butoxy dimethoxy zirconium (Zr(OCH₃)₂(OC₄H₉)₂),trimethoxy n-butoxy zirconium (Zr(OCH₃)₃(OC₄H₉)), tri-n-butoxy methoxyzirconium (Zr(OCH₃CH₂)(OC₄H₉)₃), din-butoxy diethoxy zirconium(Zr(OCH₃CH₂)₂(OC₄H₉)₂), triethoxy n-butoxy zirconium(Zr(OCH₃CH₂)₃(OC₄H₉)), and so on,

tetramethoxy hafnium (Hf(OCH₃)₄), tetraethoxy hafnium (Hf(OCH₃CH₂)₄),tetraisobutoxy hafnium (Hf(i-OC₄H₉)₄), tetran-butoxy hafnium(Hf(OC₄H₉)₄), triethoxy methoxy hafnium (Hf(OCH₃)(OCH₃CH₂)₃), diethoxydimethoxy hafnium (Hf(OCH₃)₂(OCH₃CH₂)₂), trimethoxy ethoxy hafnium(Hf(OCH₃)₃(OCH₃CH₂)), triisobutoxy methoxy hafnium (Hf(OCH₃)(i-OC₄H₉)₃),diisobutoxy dimethoxy hafnium (Hf(OCH₃)₂(i-OC₄H₉)₂), trimethoxyisobutoxy hafnium (Hf(OCH₃)₃(i-OC₄H₉)), triisobutoxy ethoxy hafnium(Hf(OCH₃CH₂)(i-OC₄H₉)₃), diisobutoxy diethoxy hafnium(Hf(OCH₃CH₂)₂(i-OC₄H₉)₂), triethoxy isobutoxy hafnium(Hf(OCH₃CH₂)₃(i-C₄H₉)), tri-n-butoxy methoxy hafnium (Hf(OCH₃)(OC₄H₉)₃),din-butoxy dimethoxy hafnium (Hf(OCH₃)₂(OC₄H₉)₂), trimethoxy n-butoxyhafnium (Hf(OCH₃)₃(OC₄H₉)), tri-n-butoxy methoxy hafnium(Hf(OCH₃CH₂)(OC₄H₉)₃), din-butoxy diethoxy hafnium(Hf(OCH₃CH₂)₂(OC₄H₉)₂), triethoxy n-butoxy hafnium(Hf(OCH₃CH₂)₃(OC₄H₉)), and so on.

As the Group IVB metal alkyl halide, exemplified is trimethyl chlorotitanium (TiCl(CH₃)₃), triethyl chloro titanium (TiCl(CH₃CH₂)₃),triisobutyl chloro titanium (TiCl(i-C₄H₉)₃), trin-butyl chloro titanium(TiCl(C₄H₉)₃), dimethyl dichloro titanium (TiCl₂(CH₃)₂), diethyldichloro titanium (TiCl₂(CH₃CH₂)₂), diisobutyl dichloro titanium(TiCl₂(i-C₄H₉)₂), trin-butyl chloro titanium (TiCl(C₄H₉)₃), methyltrichloro titanium (Ti(CH₃)Cl₃), ethyl trichloro titanium(Ti(CH₃CH₂)Cl₃), isobutyl trichloro titanium (Ti(i-C₄H₉)Cl₃), n-butyltrichloro titanium (Ti(C₄H₉)Cl₃),

trimethyl bromo titanium (TiBr(CH₃)₃), triethyl bromo titanium(TiBr(CH₃CH₂)₃), triisobutyl bromo titanium (TiBr(i-C₄H₉)₃), trin-butylbromo titanium (TiBr(C₄H₉)₃), dimethyl dibromo titanium (TiBr₂(CH₃)₂),diethyl dibromo titanium (TiBr₂(CH₃CH₂)₂), diisobutyl dibromo titanium(TiBr₂(i-C₄H₉)₂), trin-butyl bromo titanium (TiBr(C₄H₉)₃), methyltribromo titanium (Ti(CH₃)Br₃), ethyl tribromo titanium (Ti(CH₃CH₂)Br₃),isobutyl tribromo titanium (Ti(i-C₄H₉)Br₃), n-butyl tribromo titanium(Ti(C₄H₉)Br₃),

trimethyl chloro zirconium (ZrCl(CH₃)₃), triethyl chloro zirconium(ZrCl(CH₃CH₂)₃), triisobutyl chloro zirconium (ZrCl(i-C₄H₉)₃),trin-butyl chloro zirconium (ZrCl(C₄H₉)₃), dimethyl dichloro zirconium(ZrCl₂(CH₃)₂), diethyl dichloro zirconium (ZrCl₂(CH₃CH₂)₂), diisobutyldichloro zirconium (ZrCl₂(i-C₄H₉)₂), trin-butyl chloro zirconium(ZrCl(C₄H₉)₃), methyl trichloro zirconium (Zr(CH₃)Cl₃), ethyl trichlorozirconium (Zr(CH₃CH₂)Cl₃), isobutyl trichloro zirconium (Zr(i-C₄H₉)Cl₃),n-butyl trichloro zirconium (Zr(C₄H₉)Cl₃),

trimethyl bromo zirconium (ZrBr(CH₃)₃), triethyl bromo zirconium(ZrBr(CH₃CH₂)₃), triisobutyl bromo zirconium (ZrBr(i-C₄H₉)₃), trin-butylbromo zirconium (ZrBr(C₄H₉)₃), dimethyl dibromo zirconium (ZrBr₂(CH₃)₂),diethyl dibromo zirconium (ZrBr₂(CH₃CH₂)₂), diisobutyl dibromo zirconium(ZrBr₂(i-C₄H₉)₂), trin-butyl bromo zirconium (ZrBr(C₄H₉)₃), methyltribromo zirconium (Zr(CH₃)Br₃), ethyl tribromo zirconium(Zr(CH₃CH₂)Br₃), isobutyl tribromo zirconium (Zr(i-C₄H₉)Br₃), n-butyltribromo zirconium (Zr(C₄H₉)Br₃),

trimethyl chloro hafnium (HfCl(CH₃)₃), triethyl chloro hafnium(HfCl(CH₃CH₂)₃), triisobutyl chloro hafnium (HfCl(i-C₄H₉)₃), trin-butylchloro hafnium (HfCl(C₄H₉)₃), dimethyl dichloro hafnium (HfCl₂(CH₃)₂),diethyl dichloro hafnium (HfCl₂(CH₃CH₂)₂), diisobutyl dichloro hafnium(HfCl₂(i-C₄H₉)₂), trin-butyl chloro hafnium (HfCl(C₄H₉)₃), methyltrichloro hafnium (Hf(CH₃)Cl₃), ethyl trichloro hafnium (Hf(CH₃CH₂)Cl₃),isobutyl trichloro hafnium (Hf(i-C₄H₉)Cl₃), n-butyl trichloro hafnium(Hf(C₄H₉)Cl₃),

trimethyl bromo hafnium (HfBr(CH₃)₃), triethyl bromo hafnium(HfBr(CH₃CH₂)₃), triisobutyl bromo hafnium (HfBr(i-C₄H₉)₃), trin-butylbromo hafnium (HfBr(C₄H₉)₃), dimethyl dibromo hafnium (HfBr₂(CH₃)₂),diethyl dibromo hafnium (HfBr₂(CH₃CH₂)₂), diisobutyl dibromo hafnium(HfBr₂(i-C₄H₉)₂), trin-butyl bromo hafnium (HfBr(C₄H₉)₃), methyltribromo hafnium (Hf(CH₃)Br₃), ethyl tribromo hafnium (Hf(CH₃CH₂)Br₃),isobutyl tribromo hafnium (Hf(i-C₄H₉)Br₃), n-butyl tribromo hafnium(Hf(C₄H₉)Br₃).

As the Group IVB metal alkoxy halide, exemplified is trimethoxy chlorotitanium (TiCl(OCH₃)₃), triethoxy chloro titanium (TiCl(OCH₃CH₂)₃),triisobutoxy chloro titanium (TiCl(i-OC₄H₉)₃), tri-n-butoxy chlorotitanium (TiCl(OC₄H₉)₃), dimethoxy dichloro titanium (TiCl₂(OCH₃)₂),diethoxy dichloro titanium (TiCl₂(OCH₃CH₂)₂), diisobutoxy dichlorotitanium (TiCl₂(i-OC₄H₉)₂), tri-n-butoxy chloro titanium (TiCl(OC₄H₉)₃),methoxy trichloro titanium (Ti(OCH₃)Cl₃), ethoxy trichloro titanium(Ti(OCH₃CH₂)Cl₃), isobutoxy trichloro titanium (Ti(i-C₄H₉)Cl₃), n-butoxytrichloro titanium (Ti(OC₄H₉)Cl₃),

trimethoxy bromo titanium (TiBr(OCH₃)₃), triethoxy bromo titanium(TiBr(OCH₃CH₂)₃), triisobutoxy bromo titanium (TiBr(i-OC₄H₉)₃),tri-n-butoxy bromo titanium (TiBr(OC₄H₉)₃), dimethoxy dibromo titanium(TiBr₂(OCH₃)₂), diethoxy dibromo titanium (TiBr₂(OCH₃CH₂)₂), diisobutoxydibromo titanium (TiBr₂(i-OC₄H₉)₂), tri-n-butoxy bromo titanium(TiBr(OC₄H₉)₃), methoxy tribromo titanium (Ti(OCH₃)Br₃), ethoxy tribromotitanium (Ti(OCH₃CH₂)Br₃), isobutoxy tribromo titanium (Ti(i-C₄H₉)Br₃),n-butoxy tribromo titanium (Ti(OC₄H₉)Br₃),

trimethoxy chloro zirconium (ZrCl(OCH₃)₃), triethoxy chloro zirconium(ZrCl(OCH₃CH₂)₃), triisobutoxy chloro zirconium (ZrCl(i-OC₄H₉)₃),tri-n-butoxy chloro zirconium (ZrCl(OC₄H₉)₃), dimethoxy dichlorozirconium (ZrCl₂(OCH₃)₂), diethoxy dichloro zirconium (ZrCl₂(OCH₃CH₂)₂),diisobutoxy dichloro zirconium (ZrCl₂(i-OC₄H₉)₂), tri-n-butoxy chlorozirconium (ZrCl(OC₄H₉)₃), methoxy trichloro zirconium (Zr(OCH₃)Cl₃),ethoxy trichloro zirconium (Zr(OCH₃CH₂)Cl₃), isobutoxy trichlorozirconium (Zr(i-C₄H₉)Cl₃), n-butoxy trichloro zirconium (Zr(OC₄H₉)Cl₃),

trimethoxy bromo zirconium (ZrBr(OCH₃)₃), triethoxy bromo zirconium(ZrBr(OCH₃CH₂)₃), triisobutoxy bromo zirconium (ZrBr(i-OC₄H₉)₃),tri-n-butoxy bromo zirconium (ZrBr(OC₄H₉)₃), dimethoxy dibromo zirconium(ZrBr₂(OCH₃)₂), diethoxy dibromo zirconium (ZrBr₂(OCH₃CH₂)₂),diisobutoxy dibromo zirconium (ZrBr₂(i-OC₄H₉)₂), tri-n-butoxy bromozirconium (ZrBr(OC₄H₉)₃), methoxy tribromo zirconium (Zr(OCH₃)Br₃),ethoxy tribromo zirconium (Zr(OCH₃CH₂)Br₃), isobutoxy tribromo zirconium(Zr(i-C₄H₉)Br₃), n-butoxy tribromo zirconium (Zr(OC₄H₉)Br₃),

trimethoxy chloro hafnium (HfCl(OCH₃)₃), triethoxy chloro hafnium(HfCl(OCH₃CH₂)₃), triisobutoxy chloro hafnium (HfCl(i-OC₄H₉)₃),tri-n-butoxy chloro hafnium (HfCl(OC₄H₉)₃), dimethoxy dichloro hafnium(HfCl₂(OCH₃)₂), diethoxy dichloro hafnium (HfCl₂(OCH₃CH₂)₂), diisobutoxydichloro hafnium (HfCl₂(i-OC₄H₉)₂), tri-n-butoxy chloro hafnium(HfCl(OC₄H₉)₃), methoxy trichloro hafnium (Hf(OCH₃)Cl₃), ethoxytrichloro hafnium (Hf(OCH₃CH₂)Cl₃), isobutoxy trichloro hafnium(Hf(i-C₄H₉)Cl₃), n-butoxy trichloro hafnium (Hf(OC₄H₉)Cl₃),

trimethoxy bromo hafnium (HfBr(OCH₃)₃), triethoxy bromo hafnium(HfBr(OCH₃CH₂)₃), triisobutoxy bromo hafnium (HfBr(i-OC₄H₉)₃),tri-n-butoxy bromo hafnium (HfBr(OC₄H₉)₃), dimethoxy dibromo hafnium(HfBr₂(OCH₃)₂), diethoxy dibromo hafnium (HfBr₂(OCH₃CH₂)₂), diisobutoxydibromo hafnium (HfBr₂(i-OC₄H₉)₂), tri-n-butoxy bromo hafnium(HfBr(OC₄H₉)₃), methoxy tribromo hafnium (Hf(OCH₃)Br₃), ethoxy tribromohafnium (Hf(OCH₃CH₂)Br₃), isobutoxy tribromo hafnium (Hf(i-C₄H₉)Br₃),n-butoxy tribromo hafnium (Hf(OC₄H₉)Br₃).

As the Group IVB metal compound, preference is given to the Group IVBmetal halide, such as TiCl₄, TiBr₄, ZrCl₄, ZrBr₄, HfCl₄ and HfBr₄, suchas TiCl₄ and ZrCl₄.

The Group IVB metal compound could be used with one kind or as a mixtureof two or more kinds at any ratio therebetween.

When the chemical treating agent presents as a liquid at the normaltemperature, the chemical treating agent can be used by directlydropwise adding a predetermined amount of the chemical treating agent toa reaction subject to be treated with said chemical treating agent (i.e.the aforesaid composite carrier).

When the chemical treating agent presents a solid at the normaltemperature, for ease of metering and handling, it is preferably to usesaid chemical treating agent in the form of a solution. Of course, whenthe chemical treating agent presents a liquid at the normal temperature,said chemical treating agent can be also used in the form of a solutionif needed, without any specific limitation.

In preparation of the solution of the chemical treating agent, there isno limitation as to the solvent to be used herein, as long as thesolvent is capable of dissolving the chemical treating agent.

Specifically, as the solvent, exemplified is a C₅₋₁₂ alkane or ahalogenated C₅₋₁₂ alkane, for example pentane, hexane, heptane, octane,nonane, decane, undecane, dodecane, cyclohexane, chloro pentane, chlorohexane, chloro heptane, chloro octane, chloro nonane, chloro decane,chloro undecane, chloro dodecane, chloro cyclohexane and so on,preferably pentane, hexane, decane and cyclohexane, most preferablyhexane.

The solvent could be used with one kind or as a mixture of two or morekinds at any ratio therebetween.

It is obvious that a solvent capable of extracting the magnesiumcompound is not used herein to dissolve the chemical treating agent, forexample an ether based solvent, for example tetrahydrofuran.

Further, there is no limitation as to the concentration of the chemicaltreating agent in the solution, which could be determined as needed, aslong as it is sufficient for the solution to deliver the predeterminedamount of the chemical treating agent for the chemical treatment. Asaforesaid, if the chemical treating agent presents as a liquid, it isconvenient to use said chemical treating agent as such for thetreatment, while it is also acceptable to convert it into a solutionbefore use. Generally, the molar concentration of the chemical treatingagent in its solution is, but not limiting to, 0.01 to 1.0 mol/L.

As a process for conducing the chemical treatment, exemplified is aprocess wherein, when a solid chemical treating agent (for exampleZrCl₄) is used, first of all, a solution of the chemical treating agentis prepared, then the chemical treating agent is added (preferablydropwise) at a predetermined amount to the composite carrier to betreated, or when a liquid chemical treating agent (for example TiCl₄) isused, it is acceptable to add (preferably dropwise) a predeterminedamount of the chemical treating agent as such (or after prepared into asolution) to the composite carrier. Then, the chemical treating reactioncontinues (facilitated by any stirring means, if necessary) at areaction temperature ranging from −30° C. to 60° C. (preferably −20° C.to 30° C.) for 0.5 to 24 hours, preferably 1 to 8 hours, more preferably2 to 6 hours. Then, the resultant is filtrated, washed and dried.

According to this invention, the filtrating, washing (generally for 1 to8 times, preferably 2 to 6 times, most preferably 2 to 4 times) anddrying can be conducted in a conventional manner, wherein the solventfor washing could be the same as that used for dissolving the chemicaltreating agent.

According to this invention, as the amount of the chemical treatingagent to be used, it is preferably that the ratio by molar of themagnesium compound (based on Mg, solid basis) to the chemical treatingagent (based on the Group IVB metal, for example Ti) is 1:0.01-1,preferably 1:0.01-0.50, more preferably 1:0.10-0.30.

According to a further embodiment of this invention, the present processfor producing a supported nonmetallocene catalyst further comprises astep of pre-treating the composite carrier with an assistant chemicaltreating agent selected from the group consisting of an aluminoxane, analkylaluminum and any combination thereof before treating the compositecarrier with the chemical treating agent, referred to as thepre-treating step hereinafter. Then, the chemical treating step isconducted by using the chemical treating agent in the same way asaforesaid, with the only difference of replacing the composite carrierwith the thus pre-treated composite carrier.

The assistant chemical treating agent is further described as follows.

According to this invention, as the assistant chemical treating agent,exemplified is aluminoxane and alkylaluminum.

As the aluminoxane, exemplified is a linear aluminoxane((R)(R)Al—(Al(R)—O)_(n)—O—Al(R)(R)) having the following formula (I),and a cyclic aluminoxane (—(Al(R)—O—)_(n+2)—) having the followingformula (II).

wherein the Rs are identical to or different from one another,preferably identical to one another, and each independently is selectedfrom the group consisting of a C₁-C₈ alkyl, preferably methyl, ethyl,and iso-butyl, most preferably methyl, n is an integer of 1 to 50,preferably of 10 to 30.

Specifically, the aluminoxane could be preferably selected from thegroup consisting of methyl aluminoxane, ethyl aluminoxane, isobutylaluminoxane and n-butyl aluminoxane, preferably methyl aluminoxane (MAO)and isobutyl aluminoxane (IBAO).

The aluminoxane could be used with one kind or as a mixture of two ormore kinds at any ratio therebetween.

As the alkylaluminum, exemplified is a compound having a general formula(III) as follows:Al(R)₃  (III)wherein the Rs are identical to or different from one another,preferably identical to one another, and is each independently selectedfrom the group consisting of a C₁-C₈ alkyl, preferably methyl, ethyl andiso-butyl, most preferably methyl.

Specifically, the alkylaluminum could be selected from the groupconsisting of trimethyl aluminum (Al(CH₃)₃), triethyl aluminum(Al(CH₃CH₂)₃), tripropyl aluminum (Al(C₃H₇)₃), triisobutyl aluminum(Al(i-C₄H₉)₃), tri-n-butyl aluminum (Al(C₄H₉)₃), triisoamyl aluminum(Al(i-C₅H₁₁)₃), tri-n-amyl aluminum (Al(C₅H₁₁)₃), trihexyl aluminum(Al(C₆H₁₃)₃), tri-iso-hexyl aluminum (Al(i-C₆H₁₃)₃), diethyl methylaluminum (Al(CH₃)(CH₃CH₂)₂) and ethyl dimethyl aluminum(Al(CH₃CH₂)(CH₃)₂), and the like, wherein preference is given totrimethyl aluminum, triethyl aluminum, triisobutyl aluminum andtripropyl aluminum, most preferably triethyl aluminum and triisobutylaluminum.

The alkylaluminum could be used with one kind or as a mixture of two ormore kinds at any ratio therebetween.

According to this invention, as the assistant chemical treating agent,used could be only the alkylaluminum or only the aluminoxane, or anymixture of the alkylaluminum and the aluminoxane. There is no limitationas to the ratio between any two or more components in the mixture, whichcould be determined as needed.

According to this invention, the assistant chemical treating agent isgenerally used in the form of a solution. In preparation of the solutionof the assistant chemical treating agent, there is no limitation as tothe solvent to be used herein, as long as the solvent can dissolve theassistant chemical treating agent.

Specifically, as the solvent, exemplified is a C₅₋₁₂ alkane or ahalogenated C₅₋₁₂ alkane, for example pentane, hexane, heptane, octane,nonane, decane, undecane, dodecane, cyclohexane, chloro pentane; chlorohexane, chloro heptane, chloro octane, chloro nonane, chloro decane,chloro undecane, chloro dodecane, chloro cyclohexane and so on,preferably pentane, hexane, decane and cyclohexane, most preferablyhexane.

It is obvious that a solvent capable of extracting the magnesiumcompound is not used herein to dissolve the assistant chemical treatingagent, for example an ether based solvent, for example tetrahydrofuran.

The solvent could be used with one kind or as a mixture of two or morekinds at any ratio therebetween.

Further, there is no limitation as to the concentration of the assistantchemical treating agent in the solution, which could be determined asneeded, as long as it is sufficient for the solution to deliver apredetermined amount of the assistant chemical treating agent for thepre-treatment.

As a process for conducing the pre-treatment, exemplified is a processwherein, first of all, a solution of the assistant chemical treatingagent is prepared, then at a temperature ranging from −30° C. to 60° C.(preferably −20° C. to 30° C.), the assistant chemical treating agentsolution (containing a predetermined amount of the assistant chemicaltreating agent) is metering (preferably dropwise) into the compositecarrier to be pre-treated with said assistant chemical treating agent,or the composite carrier is metering into the assistant chemicaltreating agent solution, so as to form a reaction mixture. Then, thereaction continues (facilitated by any stirring means, if necessary) for1 to 8 hours, preferably 2 to 6 hours, more preferably 3 to 4 hours.Then, the thus obtained product is separated from the reaction mixtureby filtrating, washing (for 1 to 6 times, preferably 1 to 3 times) andoptional drying. Or alternatively, the thus obtained product is directlyused in the next step (i.e. the aforesaid chemical treating step) in theform of the reaction mixture without being subject to the separationbeforehand. In this case, the reaction mixture contains a certain amountof solvent, and for this reason, the amount of the solvent involved insaid next step could be reduced accordingly.

According to this invention, as the amount of the assistant chemicaltreating agent to be used, it is preferably that the ratio by molar ofthe magnesium compound (based on Mg, on a solid basis) to the assistantchemical treating agent (based on Al) is 1:0-1.0, preferably 1:0-0.5,more preferably 1:0.1-0.5.

It is known that any of the aforementioned processes and steps ispreferably carried out under a substantial water-free and oxygen-freecondition. By substantial water-free and oxygen-free condition, it meansthat water and oxygen in the system concerned is continuously controlledto be less than 10 ppm. Further, the support nonmetallocene catalystaccording to this invention, after prepared, is usually stored under asealed condition under a slightly positive pressure before use.

According to this invention, as the amount of the nonmetallocene complexto be used, it is preferably that the ratio by molar of the magnesiumcompound (based on Mg, on a solid basis) to the nonmetallocene complexis 1:0.01-1, preferably 1:0.04-0.4, more preferably 1:0.08-0.2.

According to this invention, as the amount of the solvent for dissolvingthe magnesium compound to be used, it is preferably that the ratio ofthe magnesium compound (on a solid basis) to the solvent is 1 mol:75˜400ml, preferably 1 mol:150˜300 ml, more preferably 1 mol:200˜250 ml.

According to this invention, as the amount of the porous carrier to beused, it is preferably that the ratio by weight of the magnesiumcompound (on a solid basis) to the porous carrier is 1:0.1-20,preferably 1:0.5-10, more preferably 1:1-5.

According to this invention, as the amount of the precipitating agent tobe used, it is preferably that the ratio by volume of the precipitatingagent to the solvent for dissolving the magnesium compound is 1:0.2˜5,preferably 1:0.5˜2, more preferably 1:0.8˜1.5.

According to this invention, as the amount of the chemical treatingagent to be used, it is preferably that the ratio by molar of themagnesium compound (based on Mg, on a solid basis) to the chemicaltreating agent (based on the Group IVB metal, for example Ti) is1:0.01-1, preferably 1:0.01-0.50, more preferably 1:0.10-0.30.

According to this invention, as the amount of the assistant chemicaltreating agent to be used, it is preferably that the ratio by molar ofthe magnesium compound (based on Mg, on a solid basis) to the assistantchemical treating agent (based on Al) is 1:0-1.0, preferably 1:0-0.5,more preferably 1:0.1-0.5.

In one embodiment, this invention relates to a supported nonmetallocenecatalyst produced in line with the process according to any of the firstto fourth embodiments of this invention, also referred to as a supportednonmetallocene catalyst for olefin polymerization.

In a further embodiment according to this invention, this inventionrelates to an olefin homopolymerization/copolymerization process,wherein the supported nonmetallocene catalyst of this invention is usedas the catalyst for olefin polymerization, to homopolymerize orcopolymerize olefin(s).

In the context of the olefin homopolymerization/copolymerization processof this invention, one can directly refer to the prior art for anycontent or information that has not been expressively and specificallydescribed hereinafter, for example, the reactor for polymerization, theamount of olefin(s), the way by which the catalyst or olefin isintroduced, unnecessiating the need of detailing same further herein.

According to the present olefin homopolymerization/copolymerizationprocess, the supported nonmetallocene catalyst of this invention is usedas the main catalyst, one or more selected from the group consisting ofan aluminoxane, an alkylaluminum, a halogenated alkyl aluminum, afluoroborane, an alkylboron and an alkylboron ammonium salt is used asthe co-catalyst, to homopolymerize or copolymerize olefin.

As the way of adding the main catalyst and the co-catalyst to thepolymerization system, exemplified is a way wherein the main catalyst isadded prior to the co-catalyst, or vise versa, or the main catalyst andthe co-catalyst contact with each other by mixing and then addedaltogether, or separately but simultaneously added. As the way of addingthe main catalyst and the co-catalyst separately, exemplified is thecase wherein the main catalyst and the co-catalyst are successivelyadded to one feed line or multiple feed lines. When the main catalystand the co-catalyst are to be added separately but simultaneously,multiple feed lines are required. For a continuous polymerization, theway of simultaneously and continuously adding to multiple feed lines ispreferred, while for a batch polymerization, the way of mixing the maincatalyst and the co-catalyst with each other and then adding to one feedline altogether, or adding to a feed line the co-catalyst and thenadding the main catalyst to the same feed line, is preferred.

There is no limitation as to how to conduct the olefinhomopolymerization/copolymerization, any conventional process known to aperson skilled in the art can be used, for example, a slurry process, anemulsion process, a solution process, a bulk process or a gas phaseprocess, preferably the slurry process or the gas phase process.

According to this invention, as the olefin to be used, exemplified is aC₂ to C₁₀ mono-olefin, a diolefin, a cyclic olefin and other ethylenicunsaturated compounds.

Specifically, as the C₂ to C₁₀ mono-olefin, exemplified is ethylene,propylene, 1-butene, 1-hexene, 1-heptene, 4-methyl-1-pentene, 1-octene,1-decene, 1-undecene, 1-dodecene and styrene. As the cyclic olefin,exemplified is 1-cyclopentene and norbornene. As the diolefin,exemplified is 1,4-butadiene, 2,5-pentadiene, 1,6-hexadiene,norbornadiene and 1,7-octadiene. As the other ethylenic unsaturatedcompound, exemplified is vinyl acetate, and (meth)acrylate. Thisinvention prefers the homopolymerization of ethylene, or thecopolymerization of ethylene with propylene, 1-butene or 1-hexene.

According to this invention, by homopolymerization, it refers to thepolymerization of a single kind of olefin, by copolymerization, itrefers to the polymerization between two or more of the aforesaidolefins.

According to this invention, the co-catalyst is selected from the groupconsisting of an aluminoxane, an alkylaluminum, a halogenated alkylaluminum, a fluoroborane, an alkylboron and an alkylboron ammonium salt,such as the aluminoxane and the alkylaluminum.

As the aluminoxane, exemplified is a linear aluminoxane((R)(R)Al—(Al(R)—O)_(n)—O—Al(R)(R)) having the following formula (I-1),and a cyclic aluminoxane (—(Al(R)—O—)_(n+2)—) having the followingformula (II-1).

wherein the Rs are identical to or different from one another,preferably identical to one another, and each independently is selectedfrom the group consisting of a C₁-C₈ alkyl, preferably methyl, ethyl,and iso-butyl, most preferably methyl, n is an integer of 1 to 50,preferably of 10 to 30.

Specifically, the aluminoxane could be preferably selected from thegroup consisting of methyl aluminoxane, ethyl aluminoxane, isobutylaluminoxane and n-butyl aluminoxane, preferably methyl aluminoxane (MAO)and isobutyl aluminoxane (IBAO), most preferably methyl aluminoxane(MAO).

The aluminoxane could be used with one kind or as a mixture of two ormore kinds at any ratio therebetween.

As the alkylaluminum, exemplified is a compound having a general formula(III-1) as follows:Al(R)₃  (III-1)wherein the Rs are identical to or different from one another,preferably identical to one another, and is each independently selectedfrom the group consisting of a C₁-C₈ alkyl, preferably methyl, ethyl andiso-butyl, most preferably methyl.

Specifically, the alkylaluminum could be selected from the groupconsisting of trimethyl aluminum (Al(CH₃)₃), triethyl aluminum(Al(CH₃CH₂)₃), tripropyl aluminum (Al(C₃H₇)₃), triisobutyl aluminum(Al(i-C₄H₉)₃), tri-n-butyl aluminum (Al(C₄H₉)₃), triisoamyl aluminum(Al(i-C₅H₁₁)₃), tri-n-amyl aluminum (Al(C₅H₁₁)₃), tri-hexyl aluminum(Al(C₆H₁₃)₃), tri-iso-hexyl aluminum (Al(i-C₆H₁₃)₃), diethyl methylaluminum (Al(CH₃)(CH₃CH₂)₂) and ethyl dimethyl aluminum(Al(CH₃CH₂)(CH₃)₂), and the like, wherein preference is given totrimethyl aluminum, triethyl aluminum, triisobutyl aluminum andtripropyl aluminum, more preferably triethyl aluminum and triisobutylaluminum, most preferably triethyl aluminum.

The alkylaluminum could be used with one kind or as a mixture of two ormore kinds at any ratio therebetween.

As the halogenated alkyl aluminum, the fluoroborane, the alkylboron andthe alkylboron ammonium salt, exemplified is one conventionally used inthis field, but without any limitation thereto.

Further, according to this invention, the co-catalyst could be used withone kind or as a mixture of two or more kinds of the aforesaidco-catalysts at any ratio therebetween as needed, but without anylimitation thereto.

According to this invention, depending on how the olefinhomopolymerization/copolymerization is conducted, a solvent forpolymerization may be involved.

As the solvent for polymerization, one conventionally used in this fieldfor olefin homopolymerization/copolymerization can be used, but withoutany limitation thereto.

As the solvent for polymerization, exemplified is a C₄₋₁₀ alkane (forexample, butane, pentane, hexane, heptane, octane, nonane, or decane), ahalogenated C₁₋₁₀ alkane (for example, dichloro methane), an aromatichydrocarbon based solvent (for example toluene or xylene), and so on.Hexane is preferred for this purpose.

The solvent for polymerization could be used with one kind or as amixture of two or more kinds at any ratio therebetween.

According to this invention, the polymerization pressure under which theolefin homopolymerization/copolymerization is conducted is generallybetween 0.1 to 10 MPa, preferably 0.1 to 4 MPa, most preferably 1 to 3MPa, but without any limitation thereto. According to this invention,the polymerization temperature at which the olefinhomopolymerization/copolymerization is conducted is generally from −40°C. to 200° C., preferably 10° C. to 100° C., more preferably 40° C. to90° C., but without any limitation thereto.

Further, according to this invention, the olefinhomopolymerization/copolymerization can be conduct in the presence of orin the absence of hydrogen gas. If presents, the partial pressure ofhydrogen gas may generally account for 0.01 to 99% (preferably 0.01 to50%) of the polymerization pressure, but without any limitation thereto.

According to the olefin homopolymerization/copolymerization process ofthis invention, the ratio by molar of the co-catalyst (based on Al or B)to the supported nonmetallocene catalyst (based on the central metalatom M) is generally 1 to 1000:1, preferably 10 to 500:1, morepreferably 15 to 300:1, but without any limitation thereto.

EXAMPLE

The present invention is further illustrated by using the followingexamples, not limiting to same.

The bulk density of the polymer was measured according to the ChineseStandard GB 1636-79 (unit: g/cm³).

The content of the Group IVB metal (for example Ti) and the content ofthe Mg element in the supported nonmetallocene catalyst were determinedby the ICP-AES method, while the content of the nonmetallocene ligandwas determined by the element analysis method.

The polymerization activity of the catalyst was calculated as follows.

Upon completion of the polymerization, the polymer product in thereactor was filtered and dried, and then weighed for its weight (bymass). Then, the polymerization activity of the catalyst was expressedby a value obtained by dividing the weight of the polymer product by theweight (by mass) of the supported nonmetallocene catalyst used (unit: kgpolymer per 1 g Cat).

The molecular weights Mw, Mn and the molecular weight distribution(Mw/Mn) of the polymer were determined at a temperature of 150° C. byusing the GPC V2000 type gel permeation chromatographer (from WATERSCo., USA), with o-trichlorobenzene as the solvent.

The viscosity averaged molecular weight of the polymer was calculated asfollows.

The intrinsic viscosity of the polymer was determined according to thestandard ASTM D4020-00 by using a high temperature dilution typeUbbelohde viscometer (with a capillary inner diameter of 0.44 mm, athermostatic bath media of 300# silicon oil, the solvent for dilution ofdecalin and a temperature of 135° C.), and then the viscosity averagedmolecular weight Mv of the polymer was calculated in line with thefollowing formula.Mv=5.37×10⁴×[η]^(1.37)

wherein, η is the intrinsic viscosity.

Example I Corresponding to the First Embodiment Example I-1

Anhydrous magnesium chloride was used as the magnesium compound,tetrahydrofuran was used as the solvent for dissolving the magnesiumcompound and the nonmetallocene complex, silica gel (ES757, from theIneos Company) was used as the porous carrier, the compound representedby

was used as the nonmetallocene complex.

The silica gel was thermally activated by continuously calcinating at600° C. under a N₂ atmosphere for 4 hours before use.

5 g of the anhydrous magnesium chloride and the nonmetallocene complexwere weighted, tetrahydrofuran was added thereto to completely dissolvesame at the normal temperature. Then, the thermally activated silica gelwas added thereto, after stirring for 2 hours, the resultant wasuniformly heated to 90° C. and directly vacuum dried, to obtain thesupported nonmetallocene catalyst.

In this example, the ratio of magnesium chloride to tetrahydrofuran was1 mol:210 ml, the ratio by molar of magnesium chloride to thenonmetallocene complex was 1:0.08, and the ratio by weight of magnesiumchloride to the porous carrier was 1:2.

The thus obtained supported nonmetallocene catalyst was named asCAT-I-1.

Example I-2

Substantially the same as the Example I-1, except for the followingchanges:

The porous carrier was changed to silica gel (955, from the GraceCompany), which has been thermally activated by continuously calcinatingat 400° C. under a N₂ gas atmosphere for 8 hours.

The nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to toluene, and the magnesium compound solution wasvacuum dried at 100° C.

In this example, the ratio of the magnesium compound to toluene was 1mol:150 ml, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.15, and the ratio by weight of themagnesium compound to the porous carrier was 1:4.

The thus obtained supported nonmetallocene catalyst was named asCAT-I-2.

Example I-3

Substantially the same as the Example I-1, except for the followingchanges:

The porous carrier was changed to Al₂O₃, which has been thermallyactivated by continuously calcinating at 700° C. under a N₂ gasatmosphere for 6 hours.

The magnesium compound was changed to anhydrous magnesium bromide(MgBr₂), the nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to ethyl benzene, and the magnesium compoundsolution was vacuum dried at 110° C.

In this example, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound and the nonmetallocene complex was 1mol:250 ml, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.20, and the ratio by weight of themagnesium compound to the porous carrier was 1:1.

The thus obtained supported nonmetallocene catalyst was named asCAT-I-3.

Example I-4

Substantially the same as the Example I-1, except for the followingchanges:

The porous carrier was changed to a mixed oxide of silica and MgO (at aratio by weight of 1:1), which has been thermally activated bycontinuously calcinating at 600° C. under an Ar gas atmosphere for 4hours.

The magnesium compound was changed to ethoxy magnesium chloride(MgCl(OC₂H₅)), the nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to xylene, and the magnesium compound solution wasvacuum dried at 150° C.

In this example, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound and the nonmetallocene complex was 1mol:300 ml, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.04, and the ratio by weight of themagnesium compound to the porous carrier was 1:3.

The thus obtained supported nonmetallocene catalyst was named asCAT-I-4.

Example I-5

Substantially the same as the Example I-1, except for the followingchanges:

The porous carrier was changed to montmorillonite, which has beenthermally activated by continuously calcinating at 400° C. under a N₂gas atmosphere for 8 hours.

The magnesium compound was changed to butoxy magnesium bromide(MgBr(OC₄H₉)), the nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to diethyl benzene, and the magnesium compoundsolution was vacuum dried at 110° C.

In this example, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound and the nonmetallocene complex was 1mol:400 ml, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.30, and the ratio by weight of themagnesium compound to the porous carrier was 1:5.

The thus obtained supported nonmetallocene catalyst was named asCAT-I-5.

Example I-6

Substantially the same as the Example I-1, except for the followingchanges:

The porous carrier was changed to polystyrene, which has been thermallyactivated by continuously drying at 85° C. under a N₂ gas atmosphere for12 hours.

The magnesium compound was changed to methyl magnesium chloride

(Mg(CH₃)Cl), the nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to chloro toluene, and the magnesium compoundsolution was vacuum dried at 120° C.

In this example, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.10, and the ratio by weight of themagnesium compound to the porous carrier was 1:10.

The thus obtained supported nonmetallocene catalyst was named asCAT-I-6.

Example I-7

Substantially the same as the Example I-1, except for the followingchanges:

The porous carrier was changed to kieselguhr, which has been thermallyactivated by continuously calcinating at 500° C. under a N₂ gasatmosphere for 8 hours.

The magnesium compound was changed to ethyl magnesium chloride(Mg(C₂H₅)Cl), the nonmetallocene complex was changed to

and the magnesium compound solution was vacuum dried at 60° C.

In this example, the ratio by weight of the magnesium compound to theporous carrier was 1:0.5.

The thus obtained supported nonmetallocene catalyst was named asCAT-I-7.

Example I-8

Substantially the same as the Example I-1, except for the followingchanges:

The magnesium compound was changed to ethyl magnesium (Mg(C₂H₅)₂), thenonmetallocene complex was changed to

The thus obtained supported nonmetallocene catalyst was named asCAT-I-8.

Example I-9

Substantially the same as the Example I-1, except for the followingchanges:

The magnesium compound was changed to methyl ethoxy magnesium(Mg(OC₂H₅)(CH₃)).

The thus obtained supported nonmetallocene catalyst was named asCAT-I-9.

Example I-10

Substantially the same as the Example I-1, except for the followingchanges:

The magnesium compound was changed to ethyl n-butoxy magnesium(Mg(OC₄H₉)(C₂H₅)).

The thus obtained supported nonmetallocene catalyst was named asCAT-I-10.

Reference Example I-1-A

Substantially the same as the Example I-1, except for the followingchanges:

The ratio by molar of magnesium chloride to the nonmetallocene complexwas changed to 1:0.16.

The thus obtained catalyst was named as CAT-I-1-A.

Reference Example I-1-B

Substantially the same as the Example I-1, except for the followingchanges:

The ratio by molar of magnesium chloride to the nonmetallocene complexwas changed to 1:0.04.

The thus obtained catalyst was named as CAT-I-1-B.

Reference Example I-1-C

Substantially the same as the Example I-1, except for the followingchanges:

In preparation of the catalyst, 60 ml hexane was added to the slurry toprecipitate same, which was then filtered, washed with hexane for 3times (60 ml per time), and finally vacuum dried at 60° C.

The thus obtained catalyst was named as CAT-I-1-C.

Application Example I

The catalysts CAT-I-1 to CAT-I-9, CAT-I-1-A to CAT-I-1-C obtained fromthe aforesaid Example I series were used for ethylene homopolymerizationor copolymerization under the following conditions according to thefollowing processes respectively.

Homopolymerization: an autoclave for polymerization (5 L), a slurrypolymerization process, hexane (2.5 L) as the solvent, a totalpolymerization pressure of 1.5 MPa, a polymerization temperature of 85°C., a ratio by molar of the co-catalyst to the active metal in thecatalyst of 200, a polymerization time of 2 hours.

Specifically, 2.5 L hexane was added to the autoclave forpolymerization, and the stirring means was started. Then, 50 mg of amixture of the supported nonmetallocene catalyst and the co-catalyst wasadded thereto, and ethylene was continuously supplied thereto to keepthe total polymerization pressure constant at 1.5 MPa. Upon completionof the polymerization, the inside of the autoclave was vented to theatmosphere, and the resultant polymer product was discharged from theautoclave, and weighed for its weight (by mass) after drying. Theparticulars of the polymerization reaction and the evaluation to thepolymerization were listed in the following Table I-1.

Copolymerization: an autoclave for polymerization (5 L), a slurrypolymerization process, hexane (2.5 L) as the solvent, a totalpolymerization pressure of 1.5 MPa, a polymerization temperature of 85°C., a ratio by molar of the co-catalyst to the active metal in thecatalyst of 200, a polymerization time of 2 hours.

Specifically, 2.5 L hexane was added to the autoclave forpolymerization, and the stirring means was started. Then, 50 mg of amixture of the supported nonmetallocene catalyst and the co-catalyst wasadded thereto. Hexene-1 (50 g) was added thereto all at once as thecomonomer. Ethylene was continuously supplied thereto to keep the totalpolymerization pressure constant at 1.5 MPa. Upon completion of thepolymerization, the inside of the autoclave was vented to theatmosphere, and the resultant polymer product was discharged from theautoclave, and weighed for its weight (by mass) after drying. Theparticulars of the polymerization reaction and the evaluation to thepolymerization were listed in the following Table I-1.

TABLE I-1 The results of the olefin polymerization obtained with thesupported nonmetallocene catalysts Poly Molecular Exper- activity weightiment (kgPE/ distri- No. Catalyst No. Co-catalyst type gCat) bution 1CAT-I-1 methyl homopoly- 2.26 2.14 aluminoxane merization 2 CAT-I-1methyl copolymeri- 3.15 2.27 aluminoxane zation 3 CAT-I-1 triethylhomopoly- 1.52 2.58 aluminum merization 4 CAT-I-2 methyl homopoly- 2.732.20 aluminoxane merization 5 CAT-I-3 methyl homopoly- 4.22 2.34aluminoxane merization 6 CAT-I-4 methyl homopoly- 2.65 2.20 aluminoxanemerization 7 CAT-I-5 methyl homopoly- 1.77 2.25 aluminoxane merization 8CAT-I-6 methyl homopoly- 1.50 2.16 aluminoxane merization 9 CAT-I-7methyl homopoly- 3.75 2.24 aluminoxane merization 10 CAT-I-8 methylhomopoly- 1.65 2.16 aluminoxane merization 11 CAT-I-9 methyl homopoly-1.73 2.24 aluminoxane merization 12 CAT-I-1-A methyl homopoly- 3.75 2.10aluminoxane merization 13 CAT-I-1-B methyl homopoly- 1.02 2.15aluminoxane merization 14 CAT-I-1-C methyl homopoly- 2.02 2.14aluminoxane merization

As can be seen from the Table I-1, the polymer obtained from thepolymerization by using the supported nonmetallocene catalyst producedin line with the present process exhibits a narrow molecular weightdistribution. It is well known in this field that polyethylene producedfrom the polymerization by using a Ziegler-Natta catalyst usuallyexhibits a molecular weight distribution of about from 3 to 8.

Upon comparison of the results from the experiment No. 1 and those fromthe experiment Nos. 12 and 13 in the Table I-1, it is clear that theactivity of the catalyst increases or decreases as the amount of thenonmetallocene complex to be introduced into the catalyst increases ordecreases, while the molecular weight distribution of the polymerremains substantially unchanged. This fact indicates that the activityof the supported nonmetallocene catalyst of this invention originatesfrom the nonmetallocene complex, and the performances of the polymerobtained from the polymerization depend on it as well.

Upon comparison of the results from the experiment No. 1 and those fromthe experiment No. 14 in the Table I-1, it is clear that the catalystobtained by directing drying the slurry according to this inventionexhibits a higher activity than that obtained by filtering and washingthe slurry.

Example II Corresponding to the Second Embodiment Example II-1

Anhydrous magnesium chloride was used as the magnesium compound,tetrahydrofuran was used as the solvent for dissolving the magnesiumcompound and the nonmetallocene complex, silica gel (ES757, from theIneos Company) was used as the porous carrier, the compound representedby

was used as the nonmetallocene complex.

The silica gel was thermally activated by continuously calcinating at600° C. under a N₂ atmosphere for 4 hours before use.

5 g of the anhydrous magnesium chloride and the nonmetallocene complexwere weighted, tetrahydrofuran was added thereto to completely dissolvesame at the normal temperature. Then, the thermally activated silica gelwas added thereto, after stirring for 2 hours, hexane (as theprecipitating agent) was added thereto to precipitate same. Theresultant solid was then filtered, washed by a solvent for washing(which is the same as the precipitating agent) for 2 times (by using thesame amount as that of the precipitating agent each time) and thenuniformly heated to 90° C. and vacuum dried, to obtain the supportednonmetallocene catalyst.

In this example, the ratio of magnesium chloride to tetrahydrofuran was1 mol:210 ml, the ratio by molar of magnesium chloride to thenonmetallocene complex was 1:0.08, the ratio by weight of magnesiumchloride to the porous carrier was 1:2, and the ratio by volume of theprecipitating agent to tetrahydrofuran was 1:1.

The thus obtained supported nonmetallocene catalyst was named asCAT-II-1.

Example II-2

Substantially the same as the Example II-1, except for the followingchanges:

The porous carrier was changed to silica gel (955, from the GraceCompany), which has been thermally activated by continuously calcinatingat 400° C. under a N₂ gas atmosphere for 8 hours.

The nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to toluene, and the precipitating agent was changedto cyclohexane.

In this example, the ratio of the magnesium compound to toluene was 1mol:150 ml, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.15, the ratio by weight of the magnesiumcompound to the porous carrier was 1:4, and the ratio by volume of theprecipitating agent to the solvent for dissolving the magnesium compoundand the nonmetallocene complex was 1:2.

The thus obtained supported nonmetallocene catalyst was named asCAT-II-2.

Example II-3

Substantially the same as the Example II-1, except for the followingchanges:

The porous carrier was changed to Al₂O₃, which has been thermallyactivated by continuously calcinating at 700° C. under a N₂ gasatmosphere for 6 hours.

The magnesium compound was changed to anhydrous magnesium bromide(MgBr₂), the nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to ethyl benzene, and the precipitating agent waschanged to cycloheptane.

In this example, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound and the nonmetallocene complex was 1mol:250 ml, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.20, the ratio by weight of the magnesiumcompound to the porous carrier was 1:1, and the ratio by volume of theprecipitating agent to the solvent for dissolving the magnesium compoundand the nonmetallocene complex was 1:0.80.

The thus obtained supported nonmetallocene catalyst was named asCAT-II-3.

Example II-4

Substantially the same as the Example II-1, except for the followingchanges:

The porous carrier was changed to a mixed oxide of silica and MgO (at aratio by weight of 1:1), which has been thermally activated bycontinuously calcinating at 600° C. under an Ar gas atmosphere for 4hours.

The magnesium compound was changed to ethoxy magnesium chloride(MgCl(OC₂H₅)), the nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to xylene, and the precipitating agent was changedto decane.

In this example, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound and the nonmetallocene complex was 1mol:300 ml, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.04, the ratio by weight of the magnesiumcompound to the porous carrier was 1:3, and the ratio by volume of theprecipitating agent to the solvent for dissolving the magnesium compoundand the nonmetallocene complex was 1:2.

The thus obtained supported nonmetallocene catalyst was named asCAT-II-4.

Example II-5

Substantially the same as the Example II-1, except for the followingchanges:

The porous carrier was changed to montmorillonite, which has beenthermally activated by continuously calcinating at 400° C. under a N₂gas atmosphere for 8 hours.

The magnesium compound was changed to butoxy magnesium bromide(MgBr(OC₄H₉)), the nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to diethyl benzene.

In this example, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound and the nonmetallocene complex was 1mol:400 ml, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.30, and the ratio by weight of themagnesium compound to the porous carrier was 1:5.

The thus obtained supported nonmetallocene catalyst was named asCAT-II-5.

Example II-6

Substantially the same as the Example II-1, except for the followingchanges:

The porous carrier was changed to polystyrene, which has been thermallyactivated by continuously drying at 85° C. under a N₂ gas atmosphere for12 hours.

The magnesium compound was changed to methyl magnesium chloride(Mg(CH₃)Cl), the nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to chloro toluene.

In this example, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.10, the ratio by weight of the magnesiumcompound to the porous carrier was 1:10.

The thus obtained supported nonmetallocene catalyst was named asCAT-II-6.

Example II-7

Substantially the same as the Example II-1, except for the followingchanges:

The porous carrier was changed to kieselguhr, which has been thermallyactivated by continuously calcinating at 500° C. under a N₂ gasatmosphere for 8 hours.

The magnesium compound was changed to ethyl magnesium chloride(Mg(C₂H₅)Cl), the nonmetallocene complex was changed to

In this example, the ratio by weight of the magnesium compound to theporous carrier was 1:0.5.

The thus obtained supported nonmetallocene catalyst was named asCAT-II-7.

Example II-8

Substantially the same as the Example II-1, except for the followingchanges:

The magnesium compound was changed to ethyl magnesium (Mg(C₂H₅)₂), thenonmetallocene complex was changed to

The thus obtained supported nonmetallocene catalyst was named asCAT-II-8.

Example II-9

Substantially the same as the Example II-1, except for the followingchanges:

The magnesium compound was changed to methyl ethoxy magnesium(Mg(OC₂H₅)(CH₃)).

The thus obtained supported nonmetallocene catalyst was named asCAT-II-9.

Example II-10

Substantially the same as the Example II-1, except for the followingchanges:

The magnesium compound was changed to ethyl n-butoxy magnesium(Mg(OC₄Hg)(C₂H₅)).

The thus obtained supported nonmetallocene catalyst was named asCAT-II-10.

Reference Example II-1-A

Substantially the same as the Example II-1, except for the followingchanges:

The ratio by molar of magnesium chloride to the nonmetallocene complexwas changed to 1:0.16.

The thus obtained catalyst was named as CAT-II-1-A.

Reference Example II-1-B

Substantially the same as the Example II-1, except for the followingchanges:

The ratio by molar of magnesium chloride to the nonmetallocene complexwas changed to 1:0.04.

The thus obtained catalyst was named as CAT-II-1-B.

Application Example II

The catalysts CAT-II-1 to CAT-II-9, CAT-II-1-A to CAT-II-1-B obtainedfrom the aforesaid Example II series were used for ethylenehomopolymerization or copolymerization under the following conditionsaccording to the following processes respectively.

Homopolymerization: an autoclave for polymerization (5 L), a slurrypolymerization process, hexane (2.5 L) as the solvent, a totalpolymerization pressure of 1.5 MPa, a polymerization temperature of 85°C., a ratio by molar of the co-catalyst to the active metal in thecatalyst of 200, a polymerization time of 2 hours.

Specifically, 2.5 L hexane was added to the autoclave forpolymerization, and the stirring means was started. Then, 50 mg of amixture of the supported nonmetallocene catalyst and the co-catalyst wasadded thereto, and ethylene was continuously supplied thereto to keepthe total polymerization pressure constant at 1.5 MPa. Upon completionof the polymerization, the inside of the autoclave was vented to theatmosphere, and the resultant polymer product was discharged from theautoclave, and weighed for its weight (by mass) after drying. Theparticulars of the polymerization reaction and the evaluation to thepolymerization were listed in the following Table II-1.

Copolymerization: an autoclave for polymerization (5 L), a slurrypolymerization process, hexane (2.5 L) as the solvent, a totalpolymerization pressure of 1.5 MPa, a polymerization temperature of 85°C., a ratio by molar of the co-catalyst to the active metal in thecatalyst of 200, a polymerization time of 2 hours.

Specifically, 2.5 L hexane was added to the autoclave forpolymerization, and the stirring means was started. Then, 50 mg of amixture of the supported nonmetallocene catalyst and the co-catalyst wasadded thereto. Hexene-1 (50 g) was added thereto all at once as thecomonomer. Ethylene was continuously supplied thereto to keep the totalpolymerization pressure constant at 1.5 MPa. Upon completion of thepolymerization, the inside of the autoclave was vented to theatmosphere, and the resultant polymer product was discharged from theautoclave, and weighed for its weight (by mass) after drying. Theparticulars of the polymerization reaction and the evaluation to thepolymerization were listed in the following Table II-1.

TABLE II-1 The results of the olefin polymerization obtained with thesupported nonmetallocene catalysts Poly Molecular Exper- activity weightiment (kgPE/ distri- No. Catalyst No. Co-catalyst type gCat) bution 1CAT-II-1 methyl Homopoly- 2.02 2.14 aluminoxane merization 2 CAT-II-1methyl Copolymeri- 3.03 2.27 aluminoxane zation 3 CAT-II-1 triethylHomopoly- 1.10 2.52 aluminum merization 4 CAT-II-2 methyl Homopoly- 2.142.20 aluminoxane merization 5 CAT-II-3 methyl Homopoly- 4.00 2.34aluminoxane merization 6 CAT-II-4 methyl Homopoly- 1.63 2.20 aluminoxanemerization 7 CAT-II-5 methyl Homopoly- 1.66 2.25 aluminoxane merization8 CAT-II-6 methyl Homopoly- 1.40 2.16 aluminoxane merization 9 CAT-II-7methyl Homopoly- 3.62 2.24 aluminoxane merization 10 CAT-II-8 methylHomopoly- 1.55 2.16 aluminoxane merization 11 CAT-II-9 methyl Homopoly-1.69 2.24 aluminoxane merization 12 CAT-II-1-A methyl Homopoly- 3.572.10 aluminoxane merization 13 CAT-II-1-B methyl Homopoly- 0.99 2.15aluminoxane merization

As can be seen from the Table II-1, the polymer obtained from thepolymerization by using the supported nonmetallocene catalyst producedin line with the present process exhibits a narrow molecular weightdistribution. It is well known in this field that polyethylene producedfrom the polymerization by using a Ziegler-Natta catalyst usuallyexhibits a molecular weight distribution of about from 3 to 8.

Upon comparison of the results from the experiment No. 1 and those fromthe experiment Nos. 12 and 13 in the Table II-1, it is clear that theactivity of the catalyst increases or decreases as the amount of thenonmetallocene complex to be introduced into the catalyst increases ordecreases, while the molecular weight distribution of the polymerremains substantially unchanged. This fact indicates that the activityof the supported nonmetallocene catalyst of this invention originatesfrom the nonmetallocene complex, and the performances of the polymerobtained from the polymerization depend on it as well.

Example III Corresponding to the Third Embodiment Example III-1

Anhydrous magnesium chloride was used as the magnesium compound,tetrahydrofuran was used as the solvent for dissolving the magnesiumcompound and the nonmetallocene complex, titanium tetrachloride was usedas the chemical treating agent, silica gel (ES757, from the IneosCompany) was used as the porous carrier, the compound represented by

was used as the nonmetallocene complex.

The silica gel was thermally activated by continuously calcinating at600° C. under a N₂ atmosphere for 4 hours before use.

5 g of the anhydrous magnesium chloride and the nonmetallocene complexwere weighted, tetrahydrofuran was added thereto to completely dissolvesame at the normal temperature. Then, the thermally activated silica gelwas added thereto, after stirring for 2 hours, the resultant wasuniformly heated to 90° C. and directly vacuum dried, to obtain thecomposite carrier.

Then, to the composite carrier, 60 ml hexane was added, and thentitanium tetrachloride was dropwise added thereto under stirring over aperiod of 30 minutes. The reaction continued at 60° C. under stirringfor 4 hours, then filtered, washed with hexane for 2 times (60 ml eachtime), and vacuum dried at the normal temperature to obtain thesupported nonmetallocene catalyst.

In this example, the ratio of magnesium chloride to tetrahydrofuran was1 mol:210 ml, the ratio by molar of magnesium chloride to thenonmetallocene complex was 1:0.08, the ratio by weight of magnesiumchloride to the porous carrier was 1:2, and the ratio by molar ofmagnesium chloride to titanium tetrachloride was 1:0.15.

The thus obtained supported nonmetallocene catalyst was named asCAT-III-1.

Example III-1-1

Substantially the same as the Example III-1, except for the followingchanges:

The porous carrier was changed to silica gel (955, from the GraceCompany), which has been thermally activated by continuously calcinatingat 400° C. under a N₂ gas atmosphere for 8 hours.

The nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to toluene, and the chemical treating agent waschanged to zirconium tetrachloride (ZrCl₄).

In this example, the ratio of the magnesium compound to toluene was 1mol:150 ml, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.15, the ratio by weight of the magnesiumcompound to the porous carrier was 1:4, and the ratio by molar of themagnesium compound to the chemical treating agent was 1:0.20.

The thus obtained supported nonmetallocene catalyst was named asCAT-III-1-1.

Example III-1-2

Substantially the same as the Example III-1, except for the followingchanges:

The porous carrier was changed to Al₂O₃, which has been thermallyactivated by continuously calcinating at 700° C. under a N₂ gasatmosphere for 6 hours.

The magnesium compound was changed to anhydrous magnesium bromide(MgBr₂), the nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to ethyl benzene, and the chemical treating agentwas changed to titanium tetrabromide (TiBr₄).

In this example, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound and the nonmetallocene complex was 1mol:250 ml, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.2, the ratio by weight of the magnesiumcompound to the porous carrier was 1:1, and the ratio by molar of themagnesium compound to the chemical treating agent was 1:0.30.

The thus obtained supported nonmetallocene catalyst was named asCAT-III-1-2.

Example III-1-3

Substantially the same as the Example III-1, except for the followingchanges:

The porous carrier was changed to a mixed oxide of silica and MgO (at aratio by weight of 1:1), which has been thermally activated bycontinuously calcinating at 600° C. under an Ar gas atmosphere for 4hours.

The magnesium compound was changed to ethoxy magnesium chloride(MgCl(OC₂H₅)), the nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to xylene, and the chemical treating agent waschanged to tetraethyl titanium (Ti(CH₃CH₂)₄).

In this example, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound and the nonmetallocene complex was 1mol:300 ml, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.04, and the ratio by weight of themagnesium compound to the porous carrier was 1:3, and the ratio by molarof the magnesium compound to the chemical treating agent was 1:0.05.

The thus obtained supported nonmetallocene catalyst was named asCAT-III-1-3.

Example III-1-4

Substantially the same as the Example III-1, except for the followingchanges:

The porous carrier was changed to montmorillonite, which has beenthermally activated by continuously calcinating at 400° C. under a N₂gas atmosphere for 8 hours.

The magnesium compound was changed to butoxy magnesium bromide(MgBr(OC₄H₉)), the nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to diethyl benzene, and the chemical treating agentwas changed to tetran-butyl titanium (Ti(C₄H₉)₄).

In this example, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound and the nonmetallocene complex was 1mol:400 ml, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.30, the ratio by weight of the magnesiumcompound to the porous carrier was 1:5, and the ratio by molar of themagnesium compound to the chemical treating agent was 1:0.50.

The thus obtained supported nonmetallocene catalyst was named asCAT-III-4.

Example III-1-5

Substantially the same as the Example III-1, except for the followingchanges:

The porous carrier was changed to polystyrene, which has been thermallyactivated by continuously drying at 85° C. under a N₂ gas atmosphere for12 hours.

The magnesium compound was changed to methyl magnesium chloride(Mg(CH₃)Cl), the nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to chloro toluene, and the chemical treating agentwas changed to tetraethyl zirconium (Zr(CH₃CH₂)₄).

In this example, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.10, the ratio by weight of the magnesiumcompound to the porous carrier was 1:10, and the ratio by molar of themagnesium compound to the chemical treating agent was 1:0.10.

The thus obtained supported nonmetallocene catalyst was named asCAT-III-1-5.

Example III-1-6

Substantially the same as the Example III-1, except for the followingchanges:

The porous carrier was changed to kieselguhr, which has been thermallyactivated by continuously calcinating at 500° C. under a N₂ gasatmosphere for 8 hours.

The magnesium compound was changed to ethyl magnesium chloride(Mg(C₂H₅)Cl), the nonmetallocene complex was changed to

and the chemical treating agent was changed to tetraethoxy titanium(Ti(OCH₃CH₂)₄).

In this example, the ratio by weight of the magnesium compound to theporous carrier was 1:0.5.

The thus obtained supported nonmetallocene catalyst was named asCAT-III-1-6.

Example III-1-7

Substantially the same as the Example III-1, except for the followingchanges:

The magnesium compound was changed to ethyl magnesium (Mg(C₂H₅)₂), thenonmetallocene complex was changed to

and the chemical treating agent was changed to isobutyl trichlorotitanium (Ti(i-C₄H₉)Cl₃).

The thus obtained supported nonmetallocene catalyst was named asCAT-III-1-7.

Example III-1-8

Substantially the same as the Example III-1, except for the followingchanges:

The magnesium compound was changed to methyl ethoxy magnesium(Mg(OC₂H₅)(CH₃)), and the chemical treating agent was changed totriisobutoxy chloro titanium (TiCl(i-OC₄H₉)₃).

The thus obtained supported nonmetallocene catalyst was named asCAT-III-1-8.

Example III-1-9

Substantially the same as the Example III-1, except for the followingchanges:

The magnesium compound was changed to ethyl n-butoxy magnesium(Mg(OC₄H₉)(C₂H₅)), and the chemical treating agent was changed todimethoxy dichloro zirconium (ZrCl₂(OCH₃)₂).

The thus obtained supported nonmetallocene catalyst was named asCAT-III-1-9.

Example III-2

Anhydrous magnesium chloride was used as the magnesium compound,tetrahydrofuran was used as the solvent for dissolving the magnesiumcompound and the nonmetallocene complex, titanium tetrachloride was usedas the chemical treating agent, silica gel (ES757, from the IneosCompany) was used as the porous carrier, the compound represented by

was used as the nonmetallocene complex.

The silica gel was thermally activated by continuously calcinating at600° C. under a N₂ atmosphere for 4 hours before use.

5 g of the anhydrous magnesium chloride and the nonmetallocene complexwere weighted, tetrahydrofuran was added thereto to completely dissolvesame at the normal temperature. Then, the thermally activated silica gelwas added thereto, after stirring for 2 hours, the resultant wasuniformly heated to 90° C. and directly vacuum dried, to obtain thecomposite carrier.

Then, to the composite carrier, 60 ml hexane was added, and thentriethyl aluminum (as the assistant chemical treating agent, at aconcentration of 15 wt % in hexane) was dropwise added thereto understirring over a period of 30 minutes. The reaction continued at 60° C.under stirring for 4 hours, then filtered, washed with hexane for 2times (60 ml each time), and vacuum dried at the normal temperature.

Then, to the thus pre-treated composite carrier, 60 ml hexane was added,and then titanium tetrachloride was dropwise added thereto understirring over a period of 30 minutes. The reaction continued at 60° C.under stirring for 4 hours, then filtered, washed with hexane for 2times (60 ml each time), and vacuum dried at the normal temperature toobtain the supported nonmetallocene catalyst.

In this example, the ratio of magnesium chloride to tetrahydrofuran was1 mol:210 ml, the ratio by molar of magnesium chloride to thenonmetallocene complex was 1:0.08, the ratio by weight of magnesiumchloride to the porous carrier was 1:2, the ratio by molar of magnesiumchloride to triethyl aluminum was 1:0.15, and the ratio by molar ofmagnesium chloride to titanium tetrachloride was 1:0.15.

The thus obtained supported nonmetallocene catalyst was named asCAT-III-2.

Example III-2-1

Substantially the same as the Example III-2, except for the followingchanges:

The porous carrier was changed to silica gel (955, from the GraceCompany), which has been thermally activated by continuously calcinatingat 400° C. under a N₂ gas atmosphere for 8 hours.

The nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to toluene, the assistant chemical treating agentwas changed to methyl aluminoxane (MAO, a 10 wt % solution in toluene),and the chemical treating agent was changed to zirconium tetrachloride(ZrCl₄).

After pre-treated with the assistant chemical treating agent, theresultant was washed with toluene for 3 times.

In this example, the ratio of the magnesium compound to toluene was 1mol:150 ml, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.15, the ratio by weight of the magnesiumcompound to the porous carrier was 1:4, the ratio by molar of themagnesium compound to the assistant chemical treating agent was 1:0.15,and the ratio by molar of the magnesium compound to the chemicaltreating agent was 1:0.20.

The thus obtained supported nonmetallocene catalyst was named asCAT-III-2-1.

Example III-2-2

Substantially the same as the Example III-2, except for the followingchanges:

The porous carrier was changed to Al₂O₃, which has been thermallyactivated by continuously calcinating at 700° C. under a N₂ gasatmosphere for 6 hours.

The magnesium compound was changed to anhydrous magnesium bromide(MgBr₂), the nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to ethyl benzene, the assistant chemical treatingagent was changed to trimethyl aluminum (Al(CH₃)₃), and the chemicaltreating agent was changed to titanium tetrabromide (TiBr₄).

In this example, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound and the nonmetallocene complex was 1mol:250 ml, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.2, the ratio by weight of the magnesiumcompound to the porous carrier was 1:1, the ratio by molar of themagnesium compound to the assistant chemical treating agent was 1:0.30,and the ratio by molar of the magnesium compound to the chemicaltreating agent was 1:0.30.

The thus obtained supported nonmetallocene catalyst was named asCAT-III-2-2.

Example III-2-3

Substantially the same as the Example III-2, except for the followingchanges:

The porous carrier was changed to a mixed oxide of silica and MgO (at aratio by weight of 1:1), which has been thermally activated bycontinuously calcinating at 600° C. under an Ar gas atmosphere for 4hours.

The magnesium compound was changed to ethoxy magnesium chloride(MgCl(OC₂H₅)), the nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to xylene, the assistant chemical treating agent waschanged to triisobutyl aluminum (Al(i-C₄H₉)₃), and the chemical treatingagent was changed to tetraethyl titanium (Ti(CH₃CH₂)₄).

In this example, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound and the nonmetallocene complex was 1mol:300 ml, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.04, and the ratio by weight of themagnesium compound to the porous carrier was 1:3, the ratio by molar ofthe magnesium compound to the assistant chemical treating agent was1:0.05, and the ratio by molar of the magnesium compound to the chemicaltreating agent was 1:0.05.

The thus obtained supported nonmetallocene catalyst was named asCAT-III-2-3.

Example III-2-4

Substantially the same as the Example III-2, except for the followingchanges:

The porous carrier was changed to montmorillonite, which has beenthermally activated by continuously calcinating at 400° C. under a N₂gas atmosphere for 8 hours.

The magnesium compound was changed to butoxy magnesium bromide(MgBr(OC₄H₉)), the nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to diethyl benzene, the assistant chemical treatingagent was changed to isobutyl aluminoxane, and the chemical treatingagent was changed to tetran-butyl titanium (Ti(C₄H₉)₄).

In this example, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound and the nonmetallocene complex was 1mol:400 ml, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.30, the ratio by weight of the magnesiumcompound to the porous carrier was 1:5, the ratio by molar of themagnesium compound to the assistant chemical treating agent was 1:0.50,and the ratio by molar of the magnesium compound to the chemicaltreating agent was 1:0.50.

The thus obtained supported nonmetallocene catalyst was named asCAT-III-2-4.

Example III-2-5

Substantially the same as the Example III-2, except for the followingchanges:

The porous carrier was changed to polystyrene, which has been thermallyactivated by continuously drying at 85° C. under a N₂ gas atmosphere for12 hours.

The magnesium compound was changed to methyl magnesium chloride(Mg(CH₃)Cl), the solvent for dissolving the magnesium compound and thenonmetallocene complex was changed to chloro toluene, the assistantchemical treating agent was changed to diethyl methyl aluminum(Al(CH₃)(CH₃CH₂)₂), and the chemical treating agent was changed totetraethyl zirconium (Zr(CH₃CH₂)₄).

In this example, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.10, the ratio by weight of the magnesiumcompound to the porous carrier was 1:10, the ratio by molar of themagnesium compound to the assistant chemical treating agent was 1:0.10,and the ratio by molar of the magnesium compound to the chemicaltreating agent was 1:0.10.

The thus obtained supported nonmetallocene catalyst was named asCAT-III-2-5.

Reference Example III-1-A

Substantially the same as the Example III-1, except for the followingchanges:

No nonmetallocene complex was used.

The thus obtained catalyst was named as CAT-III-1-A.

Reference Example III-1-B

Substantially the same as the Example III-1, except for the followingchanges:

The ratio by molar of magnesium chloride to the nonmetallocene complexwas changed to 1:0.16.

The thus obtained catalyst was named as CAT-III-1-B.

Reference Example III-1-C

Substantially the same as the Example III-1, except for the followingchanges:

The ratio by molar of magnesium chloride to the nonmetallocene complexwas changed to 1:0.04.

The thus obtained catalyst was named as CAT-III-1-C.

Reference Example III-1-D

Substantially the same as the Example III-1, except for the followingchanges:

The composite carrier was not treated by titanium tetrachloride.

The thus obtained catalyst was named as CAT-III-1-D.

Reference Example III-1-E

Substantially the same as the Example III-1, except for the followingchanges:

In preparation of the composite carrier, 60 ml hexane was added to theslurry to precipitate same, which was then filtered, washed with hexanefor 3 times (60 ml per time), and finally vacuum dried at 60° C.

The thus obtained catalyst was named as CAT-III-1-E.

Example III-3 Application Example

The catalysts CAT-III-1, CAT-II-2, CAT-III-1-1 to CAT-III-1-5,CAT-III-2-5, CAT-III-1-A to CAT-III-1-E obtained from the aforesaidExample III series were used for ethylenehomopolymerization/copolymerization and ultra high molecular weightpolyethylene preparation under the following conditions according to thefollowing processes respectively.

Homopolymerization: an autoclave for polymerization (5 L), a slurrypolymerization process, hexane (2.5 L) as the solvent, a totalpolymerization pressure of 0.8 MPa, a polymerization temperature of 85°C., a partial pressure of hydrogen gas of 0.2 MPa, a polymerization timeof 2 hours.

Specifically, 2.5 L hexane was added to the autoclave forpolymerization, and the stirring means was started. Then, 50 mg of amixture of the supported nonmetallocene catalyst and the co-catalyst wasadded thereto, and then hydrogen gas was supplied thereto till 0.2 MPa,and finally ethylene was continuously supplied thereto to keep the totalpolymerization pressure constant at 0.8 MPa. Upon completion of thepolymerization, the inside of the autoclave was vented to theatmosphere, and the resultant polymer product was discharged from theautoclave, and weighed for its weight (by mass) after drying. Theparticulars of the polymerization reaction and the evaluation to thepolymerization were listed in the following Table III-1.

Copolymerization: an autoclave for polymerization (5 L), a slurrypolymerization process, hexane (2.5 L) as the solvent, a totalpolymerization pressure of 0.8 MPa, a polymerization temperature of 85°C., a partial pressure of hydrogen gas of 0.2 MPa, a polymerization timeof 2 hours.

Specifically, 2.5 L hexane was added to the autoclave forpolymerization, and the stirring means was started. Then, 50 mg of amixture of the supported nonmetallocene catalyst and the co-catalyst wasadded thereto. Hexene-1 (50 g) was added thereto all at once as thecomonomer, and then hydrogen gas was supplied thereto till 0.2 MPa, andfinally ethylene was continuously supplied thereto to keep the totalpolymerization pressure constant at 0.8 MPa. Upon completion of thepolymerization, the inside of the autoclave was vented to theatmosphere, and the resultant polymer product was discharged from theautoclave, and weighed for its weight (by mass) after drying. Theparticulars of the polymerization reaction and the evaluation to thepolymerization were listed in the following Table III-1.

Preparation of ultra high molecular weight polyethylene: an autoclavefor polymerization (5 L), a slurry polymerization process, hexane (2.5L) as the solvent, a total polymerization pressure of 0.5 MPa, apolymerization temperature of 70° C., a ratio by molar of theco-catalyst to the active metal in the catalyst of 100, a polymerizationtime of 6 hours.

Specifically, 2.5 L hexane was added to the autoclave forpolymerization, and the stirring means was started. Then, 50 mg of amixture of the supported nonmetallocene catalyst and the co-catalyst wasadded thereto, and finally ethylene was continuously supplied thereto tokeep the total polymerization pressure constant at 0.5 MPa. Uponcompletion of the polymerization, the inside of the autoclave was ventedto the atmosphere, and the resultant polymer product was discharged fromthe autoclave, and weighed for its weight (by mass) after drying. Theparticulars of the polymerization reaction and the evaluation to thepolymerization were listed in the following Table III-2.

TABLE III-1 The results of the olefin polymerization obtained with thesupported nonmetallocene catalysts ratio by molar of MolecularExperiment co-catalyst to Poly activity Bulk density weight No. CatalystNo. Co-catalyst active metal type (kgPE/gCat) (g/cm³) distribution 1CAT-III-1 triethyl 100 homopolymerization 6.30 0.31 3.13 aluminum 2CAT-III-1 methyl 100 homopolymerization 4.15 0.33 2.75 aluminoxane 3CAT-III-1 triethyl 100 copolymerization 8.36 0.33 3.34 aluminum 4CAT-III-1 triethyl 500 copolymerization 8.61 0.33 3.22 aluminum 5CAT-III-1-1 triethyl 100 homopolymerization 2.74 0.26 — aluminum 6CAT-III-1-2 triethyl 100 homopolymerization 6.54 0.29 — aluminum 7CAT-III-1-3 triethyl 100 homopolymerization 3.06 0.27 — aluminum 8CAT-III-1-4 triethyl 100 homopolymerization 2.16 0.26 — aluminum 9CAT-III-1-5 triethyl 100 homopolymerization 2.47 0.30 — aluminum 10CAT-III-2 triethyl 100 homopolymerization 7.17 0.33 2.94 aluminum 11CAT-III-2 methyl 100 homopolymerization 4.64 0.35 2.67 aluminoxane 12CAT-III-2 triethyl 100 copolymerization 8.82 0.32 3.20 aluminum 13CAT-III-2-1 triethyl 100 homopolymerization 3.16 0.27 — aluminum 14CAT-III-2-2 triethyl 100 homopolymerization 5.07 030 — aluminum 15CAT-III-2-3 triethyl 100 homopolymerization 3.55 0.29 — aluminum 16CAT-III-2-4 triethyl 100 homopolymerization 2.68 0.28 — aluminum 17CAT-III-2-5 triethyl 100 homopolymerization 6.11 0.31 — aluminum 18CAT-III-1-A triethyl 100 homopolymerization 4.77 0.30 4.75 aluminum 19CAT-III-1-B triethyl 100 homopolymerization 7.44 0.34 2.84 aluminum 20CAT-III-1-C triethyl 100 homopolymerization 5.19 0.31 3.76 aluminum 21CAT-III-1-D triethyl 100 homopolymerization 1.52 0.26 2.58 aluminum 22CAT-III-1-E triethyl 100 homopolymerization 5.83 0.31 3.04 aluminum

TABLE III-2 The results of the ultra high molecular weight polyethylenepreparation obtained with the supported nonmetallocene catalysts Exper-Poly Bulk Mv iment activity density (10⁴ No. Catalyst No. Co-catalyst(kgPE/gCat) (g/cm³) g/mol) 1 CAT-III-1 triethyl 8.84 0.36 420 aluminum 2CAT-III-1 methyl 6.32 0.38 475 aluminoxane 3 CAT-III-2 triethyl 10.410.37 450 aluminum 4 CAT-III-2 methyl 9.45 0.39 522 aluminoxane 5CAT-III-1-A triethyl 5.44 0.33 294 aluminum 6 CAT-III-1-B triethyl 9.770.35 480 aluminum 7 CAT-III-1-C triethyl 6.25 0.35 365 aluminum 8CAT-III-1-D triethyl 2.92 0.27 575 aluminum 9 CAT-III-1-E triethyl 8.270.36 440 aluminum

As can be seen from the results of the experiment Nos. 3 and 4 in theTable III-1, increasing the amount of the co-catalyst to be used (i.e.increasing the ratio by molar of the co-catalyst to the active metal inthe catalyst) will not significantly change the polymerization activityand the bulk density of the polymer. This fact indicates that a highactivity for olefin polymerization can be obtained with a relativelyless amount of the co-catalyst when the supported nonmetallocenecatalyst produced in line with the process of this invention is usedherein, and the resultant polymer product (for example polyethylene)exhibits superior polymer morphology and a high polymer bulk density.

Upon comparison of the results of the experiment No. 1 and those of theexperiment No. 3, the results of the experiment No. 10 and those of theexperiment No. 12, in the Table III-1, it is clear that in case ofcopolymerization, the polymerization activity increases significantly.This fact indicates that the supported nonmetallocene catalyst producedin line with the process of this invention exhibits a relativelysignificant co-monomer effect.

Upon comparison of the results from the experiment No. 1 and those fromthe reference example experiment Nos. 18 to 21 in the Table III-1, it isclear that the activity of the catalyst increases or decreases as theamount of the nonmetallocene complex to be introduced into the catalystincreases or decreases, while the molecular weight distribution of thepolymer narrows or broadens accordingly. Further, the activity of thecatalyst increases or decreases as the amount of the chemical treatingagent to be introduced into the catalyst increases or decreases, whilethe molecular weight distribution of the polymer broadens or narrowsaccordingly. This fact indicates that the nonmetallocene complex shows afunction of narrowing the molecular weight distribution of the polymer,while the chemical treating agent shows a function of increasing theactivity of the catalyst and broadening the molecular weightdistribution of the polymer. For this reason, different catalysts interms of activity and polymer performances can be obtained with thisinvention by altering the ratio between these two components.

As can be seen from the Table III-2, it is possible to prepare an ultrahigh molecular weight polyethylene (with to some degree increased bulkdensity) by using the catalyst according to this invention. Uponcomparison of the results from the experiment No. 1 and those from theexperiment No. 2, the results from the experiment No. 3 and those fromthe experiment No. 4, it is clear that the viscosity averaged molecularweight of the polymer can be increased by using MAO as the co-catalyst.Upon comparison of the results from the experiment No. 1 and those fromthe reference example experiment Nos. 5 to 8 in the Table III-2, it isclear that the viscosity averaged molecular weight of the polymerincreases or decreases as the amount of the nonmetallocene complex to beintroduced into the catalyst increases or decreases. This fact indicatesthat the nonmetallocene complex further shows a function of increasingthe viscosity averaged molecular weight of the polymer.

As can be seen from the results of the experiment Nos. 1, 18 and 21 inthe Table III-1 and those of the experiment Nos. 1, 5 and 8 in the TableIII-2, the catalyst obtained with the case wherein only nonmetallocenecomplex was used in preparation of the supported nonmetallocenecatalyst, or that obtained with the case wherein only chemical treatingagent was used in preparation of the supported nonmetallocene catalyst,shows lowered activity than that obtained with the case wherein both ofthe nonmetallocene complex and the chemical treating agent were used inpreparation of the supported nonmetallocene catalyst. This factindicates that the supported nonmetallocene catalyst produced in linewith the process of this invention necessarily involves a synergiceffect. That is, the activity observed with the case wherein bothcomponents exist is higher than that observed with the case wherein onlyeither component exists.

Upon comparison of the results from the experiment No. 1 and those fromthe experiment No. 22 in the Table III-1, and the results of theexperiment No. 1 and those from the experiment No. 9 in the Table III-2,it is clear that the catalyst obtained by directing drying the slurryexhibits a higher activity than that obtained by filtering and washingthe slurry.

Example IV Corresponding to the Fourth Embodiment Example IV-1

Anhydrous magnesium chloride was used as the magnesium compound,tetrahydrofuran was used as the solvent for dissolving the magnesiumcompound and the nonmetallocene complex, titanium tetrachloride was usedas the chemical treating agent, silica gel (ES757, from the IneosCompany) was used as the porous carrier, the compound represented by

was used as the nonmetallocene complex.

The silica gel was thermally activated by continuously calcinating at600° C. under a N₂ atmosphere for 4 hours before use.

5 g of the anhydrous magnesium chloride and the nonmetallocene complexwere weighted, tetrahydrofuran was added thereto to completely dissolvesame at the normal temperature. Then, the thermally activated silica gelwas added thereto, after stirring for 2 hours, hexane (as theprecipitating agent) was added thereto to precipitate same. Theresultant solid was then filtered, washed by a solvent for washing(which is the same as the precipitating agent) for 2 times (by using thesame amount as that of the precipitating agent each time) and thenuniformly heated to 60° C. and vacuum dried, to obtain the compositecarrier.

Then, to the composite carrier, 60 ml hexane was added, and thentitanium tetrachloride was dropwise added thereto under stirring over aperiod of 30 minutes. The reaction continued at 60° C. under stirringfor 4 hours, then filtered, washed with hexane for 2 times (60 ml eachtime), and vacuum dried at the normal temperature to obtain thesupported nonmetallocene catalyst.

In this example, the ratio of magnesium chloride to tetrahydrofuran was1 mol:210 ml, the ratio by molar of magnesium chloride to thenonmetallocene complex was 1:0.07, the ratio by weight of magnesiumchloride to the porous carrier was 1:2, the ratio by volume of theprecipitating agent to tetrahydrofuran was 1:1, and the ratio by molarof magnesium chloride to titanium tetrachloride was 1:0.15.

The thus obtained supported nonmetallocene catalyst was named asCAT-IV-1.

Example IV-1-1

Substantially the same as the Example IV-1, except for the followingchanges:

The porous carrier was changed to silica gel (955, from the GraceCompany), which has been thermally activated by continuously calcinatingat 400° C. under a N₂ gas atmosphere for 8 hours.

The nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to toluene, the precipitating agent was changed tocyclohexane, and the chemical treating agent was changed to zirconiumtetrachloride (ZrCl₄).

In this example, the ratio of the magnesium compound to toluene was 1mol:150 ml, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.15, the ratio by weight of the magnesiumcompound to the porous carrier was 1:4, the ratio by volume of theprecipitating agent to the solvent for dissolving the magnesium compoundand the nonmetallocene complex was 1:2, and the ratio by molar of themagnesium compound to the chemical treating agent was 1:0.20.

The thus obtained supported nonmetallocene catalyst was named asCAT-IV-1-1.

Example IV-1-2

Substantially the same as the Example IV-1, except for the followingchanges:

The porous carrier was changed to Al₂O₃, which has been thermallyactivated by continuously calcinating at 700° C. under a N₂ gasatmosphere for 6 hours.

The magnesium compound was changed to anhydrous magnesium bromide(MgBr₂), the nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to ethyl benzene, the precipitating agent waschanged to cycloheptane, and the chemical treating agent was changed totitanium tetrabromide (TiBr₄).

In this example, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound and the nonmetallocene complex was 1mol:250 ml, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.2, the ratio by weight of the magnesiumcompound to the porous carrier was 1:1, the ratio by volume of theprecipitating agent to the solvent for dissolving the magnesium compoundand the nonmetallocene complex was 1:0.7, and the ratio by molar of themagnesium compound to the chemical treating agent was 1:0.30.

The thus obtained supported nonmetallocene catalyst was named asCAT-IV-1-2.

Example IV-1-3

Substantially the same as the Example IV-1, except for the followingchanges:

The porous carrier was changed to a mixed oxide of silica and MgO (at aratio by weight of 1:1), which has been thermally activated bycontinuously calcinating at 600° C. under an Ar gas atmosphere for 4hours.

The magnesium compound was changed to ethoxy magnesium chloride(MgCl(OC₂H₅)), the nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to xylene, the precipitating agent was changed todecane, and the chemical treating agent was changed to tetraethyltitanium (Ti(CH₃CH₂)₄).

In this example, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound and the nonmetallocene complex was 1mol:300 ml, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.04, and the ratio by weight of themagnesium compound to the porous carrier was 1:3, the ratio by volume ofthe precipitating agent to the solvent for dissolving the magnesiumcompound and the nonmetallocene complex was 1:1.5, and the ratio bymolar of the magnesium compound to the chemical treating agent was1:0.05.

The thus obtained supported nonmetallocene catalyst was named asCAT-IV-1-3.

Example IV-1-4

Substantially the same as the Example IV-1, except for the followingchanges:

The porous carrier was changed to montmorillonite, which has beenthermally activated by continuously calcinating at 400° C. under a N₂gas atmosphere for 8 hours.

The magnesium compound was changed to butoxy magnesium bromide(MgBr(OC₄H₉)), the nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to diethyl benzene, and the chemical treating agentwas changed to tetran-butyl titanium (Ti(C₄H₉)₄). In this example, theratio of the magnesium compound to the solvent for dissolving themagnesium compound and the nonmetallocene complex was 1 mol:400 ml, theratio by molar of the magnesium compound to the nonmetallocene complexwas 1:0.30, the ratio by weight of the magnesium compound to the porouscarrier was 1:5, and the ratio by molar of the magnesium compound to thechemical treating agent was 1:0.50.

The thus obtained supported nonmetallocene catalyst was named asCAT-IV-1-4.

Example IV-1-5

Substantially the same as the Example IV-1, except for the followingchanges:

The porous carrier was changed to polystyrene, which has been thermallyactivated by continuously drying at 85° C. under a N₂ gas atmosphere for12 hours.

The magnesium compound was changed to methyl magnesium chloride(Mg(CH₃)Cl), the nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to chloro toluene, and the chemical treating agentwas changed to tetraethyl zirconium (Zr(CH₃CH₂)₄).

In this example, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.10, the ratio by weight of the magnesiumcompound to the porous carrier was 1:10, and the ratio by molar of themagnesium compound to the chemical treating agent was 1:0.10.

The thus obtained supported nonmetallocene catalyst was named asCAT-IV-1-5.

Example IV-1-6

Substantially the same as the Example IV-1, except for the followingchanges:

The porous carrier was changed to kieselguhr, which has been thermallyactivated by continuously calcinating at 500° C. under a N₂ gasatmosphere for 8 hours.

The magnesium compound was changed to ethyl magnesium chloride(Mg(C₂H₅)Cl), the nonmetallocene complex was changed to

and the chemical treating agent was changed to tetraethoxy titanium(Ti(OCH₃CH₂)₄).

In this example, the ratio by weight of the magnesium compound to theporous carrier was 1:0.5.

The thus obtained supported nonmetallocene catalyst was named asCAT-IV-1-6.

Example IV-1-7

Substantially the same as the Example IV-1, except for the followingchanges:

The magnesium compound was changed to ethyl magnesium (Mg(C₂H₅)₂), thenonmetallocene complex was changed to

and the chemical treating agent was changed to isobutyl trichlorotitanium (Ti(i-C₄H₉)Cl₃).

The thus obtained supported nonmetallocene catalyst was named asCAT-IV-1-7.

Example IV-1-8

Substantially the same as the Example IV-1, except for the followingchanges:

The magnesium compound was changed to methyl ethoxy magnesium(Mg(OC₂H₅)(CH₃)), and the chemical treating agent was changed totriisobutoxy chloro titanium (TiCl(i-OC₄H₉)₃).

The thus obtained supported nonmetallocene catalyst was named asCAT-IV-1-8.

Example IV-1-9

Substantially the same as the Example IV-1, except for the followingchanges:

The magnesium compound was changed to ethyl n-butoxy magnesium(Mg(OC₄H₉)(C₂H₅)), and the chemical treating agent was changed todimethoxy dichloro zirconium (ZrCl₂(OCH₃)₂).

The thus obtained supported nonmetallocene catalyst was named asCAT-IV-1-9.

Example IV-2

Anhydrous magnesium chloride was used as the magnesium compound,tetrahydrofuran was used as the solvent for dissolving the magnesiumcompound and the nonmetallocene complex, titanium tetrachloride was usedas the chemical treating agent, silica gel (ES757, from the IneosCompany) was used as the porous carrier, the compound represented by

was used as the nonmetallocene complex.

The silica gel was thermally activated by continuously calcinating at600° C. under a N₂ atmosphere for 4 hours before use.

5 g of the anhydrous magnesium chloride and the nonmetallocene complexwere weighted, tetrahydrofuran was added thereto to completely dissolvesame at the normal temperature. Then, the thermally activated silica gelwas added thereto, after stirring for 2 hours, hexane (as theprecipitating agent) was added thereto to precipitate same. Theresultant solid was then filtered, washed by a solvent for washing(which is the same as the precipitating agent) for 2 times (by using thesame amount as that of the precipitating agent each time) and thenuniformly heated to 60° C. and vacuum dried, to obtain the compositecarrier.

Then, to the composite carrier, 60 ml hexane was added, and thentriethyl aluminum (as the assistant chemical treating agent, at aconcentration of 15 wt % in hexane) was dropwise added thereto understirring over a period of 30 minutes. The reaction continued at 60° C.under stirring for 4 hours, then filtered, washed with hexane for 2times (60 ml each time), and vacuum dried at the normal temperature.

Then, to the thus pre-treated composite carrier, 60 ml hexane was added,and then titanium tetrachloride was dropwise added thereto understirring over a period of 30 minutes. The reaction continued at 60° C.under stirring for 4 hours, then filtered, washed with hexane for 2times (60 ml each time), and vacuum dried at the normal temperature toobtain the supported nonmetallocene catalyst.

In this example, the ratio of magnesium chloride to tetrahydrofuran was1 mol:210 ml, the ratio by molar of magnesium chloride to thenonmetallocene complex was 1:0.07, the ratio by weight of magnesiumchloride to the porous carrier was 1:2, the ratio by volume of theprecipitating agent to tetrahydrofuran was 1:1, the ratio by molar ofmagnesium chloride to triethyl aluminum was 1:0.15, and the ratio bymolar of magnesium chloride to titanium tetrachloride was 1:0.15.

The thus obtained supported nonmetallocene catalyst was named asCAT-IV-2.

Example IV-2-1

Substantially the same as the Example IV-2, except for the followingchanges:

The porous carrier was changed to silica gel (955, from the GraceCompany), which has been thermally activated by continuously calcinatingat 400° C. under a N₂ gas atmosphere for 8 hours.

The nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to toluene, the precipitating agent was changed tocyclohexane, the assistant chemical treating agent was changed to methylaluminoxane (MAO, a 10 wt % solution in toluene), and the chemicaltreating agent was changed to zirconium tetrachloride (ZrCl₄).

After pre-treated with the assistant chemical treating agent, theresultant was washed with toluene for 3 times.

In this example, the ratio of the magnesium compound to toluene was 1mol:150 ml, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.15, the ratio by weight of the magnesiumcompound to the porous carrier was 1:4, the ratio by volume of theprecipitating agent to the solvent for dissolving the magnesium compoundand the nonmetallocene complex was 1:2, the ratio by molar of themagnesium compound to the assistant chemical treating agent was 1:0.15,and the ratio by molar of the magnesium compound to the chemicaltreating agent was 1:0.20.

The thus obtained supported nonmetallocene catalyst was named asCAT-IV-2-1.

Example IV-2-2

Substantially the same as the Example IV-2, except for the followingchanges:

The porous carrier was changed to Al₂O₃, which has been thermallyactivated by continuously calcinating at 700° C. under a N₂ gasatmosphere for 6 hours.

The magnesium compound was changed to anhydrous magnesium bromide(MgBr₂), the nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to ethyl benzene, the precipitating agent waschanged to cycloheptane, the assistant chemical treating agent waschanged to trimethyl aluminum (Al(CH₃)₃), and the chemical treatingagent was changed to titanium tetrabromide (TiBr₄).

In this example, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound and the nonmetallocene complex was 1mol:250 ml, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.2, the ratio by weight of the magnesiumcompound to the porous carrier was 1:1, the ratio by volume of theprecipitating agent to the solvent for dissolving the magnesium compoundand the nonmetallocene complex was 1:0.70, the ratio by molar of themagnesium compound to the assistant chemical treating agent was 1:0.30,and the ratio by molar of the magnesium compound to the chemicaltreating agent was 1:0.30.

The thus obtained supported nonmetallocene catalyst was named asCAT-IV-2-2.

Example IV-2-3

Substantially the same as the Example IV-2, except for the followingchanges:

The porous carrier was changed to a mixed oxide of silica and MgO (at aratio by weight of 1:1), which has been thermally activated bycontinuously calcinating at 600° C. under an Ar gas atmosphere for 4hours.

The magnesium compound was changed to ethoxy magnesium chloride(MgCl(OC₂H₅)), the nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to xylene, the precipitating agent was changed todecane, the assistant chemical treating agent was changed to triisobutylaluminum (Al(i-C₄H₉)₃), and the chemical treating agent was changed totetraethyl titanium (Ti(CH₃CH₂)₄).

In this example, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound and the nonmetallocene complex was 1mol:300 ml, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.04, and the ratio by weight of themagnesium compound to the porous carrier was 1:3, the ratio by volume ofthe precipitating agent to the solvent for dissolving the magnesiumcompound and the nonmetallocene complex was 1:1.5, the ratio by molar ofthe magnesium compound to the assistant chemical treating agent was1:0.05, and the ratio by molar of the magnesium compound to the chemicaltreating agent was 1:0.05.

The thus obtained supported nonmetallocene catalyst was named asCAT-IV-2-3.

Example IV-2-4

Substantially the same as the Example IV-2, except for the followingchanges:

The porous carrier was changed to montmorillonite, which has beenthermally activated by continuously calcinating at 400° C. under a N₂gas atmosphere for 8 hours.

The magnesium compound was changed to butoxy magnesium bromide(MgBr(OC₄H₉)), the nonmetallocene complex was changed to

the solvent for dissolving the magnesium compound and the nonmetallocenecomplex was changed to diethyl benzene, the assistant chemical treatingagent was changed to isobutyl aluminoxane, and the chemical treatingagent was changed to tetran-butyl titanium (Ti(C₄H₉)₄).

In this example, the ratio of the magnesium compound to the solvent fordissolving the magnesium compound and the nonmetallocene complex was 1mol:400 ml, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.30, the ratio by weight of the magnesiumcompound to the porous carrier was 1:5, the ratio by molar of themagnesium compound to the assistant chemical treating agent was 1:0.50,and the ratio by molar of the magnesium compound to the chemicaltreating agent was 1:0.50.

The thus obtained supported nonmetallocene catalyst was named asCAT-IV-2-4.

Example IV-2-5

Substantially the same as the Example IV-2, except for the followingchanges:

The porous carrier was changed to polystyrene, which has been thermallyactivated by continuously drying at 85° C. under a N₂ gas atmosphere for12 hours.

The magnesium compound was changed to methyl magnesium chloride(Mg(CH₃)Cl), the solvent for dissolving the magnesium compound and thenonmetallocene complex was changed to chloro toluene, the assistantchemical treating agent was changed to diethyl methyl aluminum(Al(CH₃)(CH₃CH₂)₂), and the chemical treating agent was changed totetraethyl zirconium (Zr(CH₃CH₂)₄).

In this example, the ratio by molar of the magnesium compound to thenonmetallocene complex was 1:0.10, the ratio by weight of the magnesiumcompound to the porous carrier was 1:10, the ratio by molar of themagnesium compound to the assistant chemical treating agent was 1:0.10,and the ratio by molar of the magnesium compound to the chemicaltreating agent was 1:0.10.

The thus obtained supported nonmetallocene catalyst was named asCAT-IV-2-5.

Reference Example IV-1-A

Substantially the same as the Example IV-1, except for the followingchanges:

No nonmetallocene complex was used.

The thus obtained catalyst was named as CAT-IV-1-A.

Reference Example IV-1-B

Substantially the same as the Example IV-1, except for the followingchanges:

The ratio by molar of magnesium chloride to the nonmetallocene complexwas changed to 1:0.14.

The thus obtained catalyst was named as CAT-IV-1-B.

Reference Example IV-1-C

Substantially the same as the Example IV-1, except for the followingchanges:

The ratio by molar of magnesium chloride to the nonmetallocene complexwas changed to 1:0.03.

The thus obtained catalyst was named as CAT-IV-1-C.

Reference Example IV-1-D

Substantially the same as the Example IV-1, except for the followingchanges:

The composite carrier was not treated by titanium tetrachloride.

The thus obtained catalyst was named as CAT-IV-1-D.

Example IV-3 Application Example

The catalysts CAT-IV-1, CAT-IV-2, CAT-IV-1-1 to CAT-IV-1-5, CAT-IV-2-5,CAT-IV-1-A to CAT-IV-1-D obtained from the aforesaid Example IV serieswere used for ethylene homopolymerization/copolymerization and ultrahigh molecular weight polyethylene preparation under the followingconditions according to the following processes respectively.

Homopolymerization: an autoclave for polymerization (5 L), a slurrypolymerization process, hexane (2.5 L) as the solvent, a totalpolymerization pressure of 0.8 MPa, a polymerization temperature of 85°C., a partial pressure of hydrogen gas of 0.2 MPa, a polymerization timeof 2 hours.

Specifically, 2.5 L hexane was added to the autoclave forpolymerization, and the stirring means was started. Then, 50 mg of amixture of the supported nonmetallocene catalyst and the co-catalyst wasadded thereto, and then hydrogen gas was supplied thereto till 0.2 MPa,and finally ethylene was continuously supplied thereto to keep the totalpolymerization pressure constant at 0.8 MPa. Upon completion of thepolymerization, the inside of the autoclave was vented to theatmosphere, and the resultant polymer product was discharged from theautoclave, and weighed for its weight (by mass) after drying. Theparticulars of the polymerization reaction and the evaluation to thepolymerization were listed in the following Table IV-1.

Copolymerization: an autoclave for polymerization (5 L), a slurrypolymerization process, hexane (2.5 L) as the solvent, a totalpolymerization pressure of 0.8 MPa, a polymerization temperature of 85°C., a partial pressure of hydrogen gas of 0.2 MPa, a polymerization timeof 2 hours.

Specifically, 2.5 L hexane was added to the autoclave forpolymerization, and the stirring means was started. Then, 50 mg of amixture of the supported nonmetallocene catalyst and the co-catalyst wasadded thereto. Hexene-1 (50 g) was added thereto all at once as thecomonomer, and then hydrogen gas was supplied thereto till 0.2 MPa, andfinally ethylene was continuously supplied thereto to keep the totalpolymerization pressure constant at 0.8 MPa. Upon completion of thepolymerization, the inside of the autoclave was vented to theatmosphere, and the resultant polymer product was discharged from theautoclave, and weighed for its weight (by mass) after drying. Theparticulars of the polymerization reaction and the evaluation to thepolymerization were listed in the following Table IV-1.

Preparation of ultra high molecular weight polyethylene: an autoclavefor polymerization (5 L), a slurry polymerization process, hexane (2.5L) as the solvent, a total polymerization pressure of 0.5 MPa, apolymerization temperature of 70° C., a ratio by molar of theco-catalyst to the active metal in the catalyst of 100, a polymerizationtime of 6 hours.

Specifically, 2.5 L hexane was added to the autoclave forpolymerization, and the stirring means was started. Then, 50 mg of amixture of the supported nonmetallocene catalyst and the co-catalyst wasadded thereto, and finally ethylene was continuously supplied thereto tokeep the total polymerization pressure constant at 0.5 MPa. Uponcompletion of the polymerization, the inside of the autoclave was ventedto the atmosphere, and the resultant polymer product was discharged fromthe autoclave, and weighed for its weight (by mass) after drying. Theparticulars of the polymerization reaction and the evaluation to thepolymerization were listed in the following Table IV-2.

TABLE IV-1 The results of the olefin polymerization obtained with thesupported nonmetallocene catalysts ratio by molar of co-catalystMolecular Experiment to active Poly activity Bulk density weight No.Catalyst No. Co-catalyst metal type (kgPE/gCat) (g/cm³) distribution 1CAT-IV-1 triethyl 100 homopolymerization 5.83 0.31 3.04 aluminum 2CAT-IV-1 methyl 100 homopolymerization 4.47 0.33 2.67 aluminoxane 3CAT-IV-1 triethyl 100 copolymerization 8.71 0.33 3.26 aluminum 4CAT-IV-1 triethyl 500 copolymerization 8.99 0.33 3.11 aluminum 5CAT-IV-1-1 triethyl 100 homopolymerization 3.17 0.26 aluminum 6CAT-IV-1-2 triethyl 100 homopolymerization 6.13 0.29 aluminum 7CAT-IV-1-3 triethyl 100 homopolymerization 3.19 0.27 aluminum 8CAT-IV-1-4 triethyl 100 homopolymerization 2.44 0.26 aluminum 9CAT-IV-1-5 triethyl 100 homopolymerization 5.86 0.30 aluminum 10CAT-IV-2 triethyl 100 homopolymerization 5.15 0.33 2.82 aluminum 11CAT-IV-2 methyl 100 homopolymerization 4.19 0.35 2.50 aluminoxane 12CAT-IV-2 triethyl 100 copolymerization 6.74 0.32 3.07 aluminum 13CAT-IV-2-1 triethyl 100 homopolymerization 3.37 0.27 aluminum 14CAT-IV-2-2 triethyl 100 homopolymerization 5.39 030 aluminum 15CAT-IV-2-3 triethyl 100 homopolymerization 3.85 0.29 aluminum 16CAT-IV-2-4 triethyl 100 homopolymerization 2.90 0.28 aluminum 17CAT-IV-2-5 triethyl 100 homopolymerization 4.63 0.31 aluminum 18CAT-IV-1-A triethyl 100 homopolymerization 5.54 0.31 4.54 aluminum 19CAT-IV-1-B triethyl 100 homopolymerization 7.77 0.34 2.73 aluminum 20CAT-IV-1-C triethyl 100 homopolymerization 5.05 0.30 3.67 aluminum 21CAT-IV-1-D triethyl 100 homopolymerization 1.10 0.26 2.52 aluminum

TABLE IV-2 The results of the ultra high molecular weight polyethylenepreparation obtained with the supported nonmetallocene catalysts Exper-Poly Bulk Mv iment activity density (10⁴ No. Catalyst No. Co-catalyst(kgPE/gCat) (g/cm³) g/mol) 1 CAT-IV-1 triethyl 8.27 0.36 440 aluminum 2CAT-IV-1 methyl 7.47 0.38 512 aluminoxane 3 CAT-IV-2 triethyl 7.72 0.37474 aluminum 4 CAT-IV-2 methyl 9.64 0.39 566 aluminoxane 5 CAT-IV-1-Atriethyl 6.89 0.35 320 aluminum 6 CAT-IV-1-B triethyl 10.14 0.35 530aluminum 7 CAT-IV-1-C triethyl 6.74 0.33 400 aluminum 8 CAT-IV-1-Dtriethyl 2.55 0.27 240 aluminum

As can be seen from the results of the experiment Nos. 3 and 4 in theTable IV-1, increasing the amount of the co-catalyst to be used (i.e.increasing the ratio by molar of the co-catalyst to the active metal inthe catalyst) will not significantly change the polymerization activityand the bulk density of the polymer. This fact indicates that a highactivity for olefin polymerization can be obtained with a relativelyless amount of the co-catalyst when the supported nonmetallocenecatalyst produced in line with the process of this invention is usedherein, and the resultant polymer product (for example polyethylene)exhibits superior polymer morphology and a high polymer bulk density.

Upon comparison of the results of the experiment No. 1 and those of theexperiment No. 3, the results of the experiment No. 10 and those of theexperiment No. 12, in the Table IV-1, it is clear that in case ofcopolymerization, the polymerization activity increases significantly.This fact indicates that the supported nonmetallocene catalyst producedin line with the process of this invention exhibits a relativelysignificant co-monomer effect.

Upon comparison of the results from the experiment No. 1 and those fromthe reference example experiment Nos. 18 to 21 in the Table IV-1, it isclear that the activity of the catalyst increases or decreases as theamount of the nonmetallocene complex to be introduced into the catalystincreases or decreases, while the molecular weight distribution of thepolymer narrows or broadens accordingly. Further, the activity of thecatalyst increases or decreases as the amount of the chemical treatingagent to be introduced into the catalyst increases or decreases, whilethe molecular weight distribution of the polymer broadens or narrowsaccordingly. This fact indicates that the nonmetallocene complex shows afunction of narrowing the molecular weight distribution of the polymer,while the chemical treating agent shows a function of increasing theactivity of the catalyst and broadening the molecular weightdistribution of the polymer. For this reason, different catalysts interms of activity and polymer performances can be obtained with thisinvention by altering the ratio between these two components.

As can be seen from the Table IV-2, it is possible to prepare an ultrahigh molecular weight polyethylene (with to some degree increased bulkdensity) by using the catalyst according to this invention. Uponcomparison of the results from the experiment No. 1 and those from theexperiment No. 2, the results from the experiment No. 3 and those fromthe experiment No. 4, it is clear that the viscosity averaged molecularweight of the polymer can be increased by using MAO as the co-catalyst.Upon comparison of the results from the experiment No. 1 and those fromthe reference example experiment Nos. 5 to 8 in the Table IV-2, it isclear that the viscosity averaged molecular weight of the polymerincreases or decreases as the amount of the nonmetallocene complex to beintroduced into the catalyst increases or decreases. This fact indicatesthat the nonmetallocene complex further shows a function of increasingthe viscosity averaged molecular weight of the polymer.

As can be seen from the results of the experiment Nos. 1, 18 and 21 inthe Table IV-1 and those of the experiment Nos. 1, 5 and 8 in the TableIV-2, the catalyst obtained with the case wherein only nonmetallocenecomplex was used in preparation of the supported nonmetallocenecatalyst, or that obtained with the case wherein only chemical treatingagent was used in preparation of the supported nonmetallocene catalyst,shows lowered activity than that obtained with the case wherein both ofthe nonmetallocene complex and the chemical treating agent were used inpreparation of the supported nonmetallocene catalyst. This factindicates that the supported nonmetallocene catalyst produced in linewith the process of this invention necessarily involves a synergiceffect. That is, the activity observed with the case wherein bothcomponents exist is higher than that observed with the case wherein onlyeither component exists.

It will be apparent to those skilled in the art that variousmodifications and variation can be made in the present invention withoutdeparting from the spirit or scope of the invention. Thus, it isintended that the present invention cover the modifications andvariations of this invention provided they come within the scope of theappended claims and their equivalents.

We claim:
 1. A process for producing a supported nonmetallocenecatalyst, comprising: dissolving at least one magnesium compound and atleast one nonmetallocene complex in at least one solvent to obtain amagnesium compound solution; mixing at least one carrier chosen from thegroup consisting of porous carriers and thermally activated porouscarriers with the magnesium compound solution to obtain a slurry; anddrying the slurry or introducing into the slurry at least oneprecipitating agent to obtain the supported nonmetallocene catalyst,wherein the nonmetallocene complex is chosen from the group consistingof the compounds having following formula,

wherein: q is 0 or 1; d is 1; m is 1, 2 or 3; M is chosen from the groupconsisting of metal atoms of Groups III to XI; n is 1, 2, 3 or 4; X ischosen from the group consisting of halogen atoms, a hydrogen atom,C₁-C₃₀ hydrocarbyl groups, substituted C₁-C₃₀ hydrocarbyl groups,oxygen-containing groups, nitrogen-containing groups, sulfur-containinggroups, boron-containing groups, aluminum-containing groups,phosphor-containing groups, silicon-containing groups,germanium-containing groups, and tin-containing groups, when multiple Xsexist, the Xs may be the same as or different from one another, and mayform a bond or a ring with one another; A is chosen from the groupconsisting of an oxygen atom, a sulfur atom, a selenium atom,

—NR²³R²⁴,

—PR²⁸R²⁹, —P(O)R³⁰OR³¹, sulfone groups, sulfoxide groups, and —Se(O)R³⁹,wherein N, O, S, Se and P in A each represents a coordination atom; B ischosen from the group consisting of a nitrogen atom, nitrogen-containinggroups, phosphor-containing groups, and C₁-C₃₀ hydrocarbylene groups; Dis chosen from the group consisting of a nitrogen atom, an oxygen atom,a sulfur atom, a selenium atom, a phosphor atom, nitrogen-containinggroups, phosphor-containing groups, C₁-C₃₀ hydrocarbylene group, sulfonegroup, sulfoxide groups,

and —P(O)R³²(OR³³), wherein N, O, S, Se and P in D each represents acoordination atom; E is chosen from the group consisting ofnitrogen-containing groups, oxygen-containing groups, sulfur-containinggroups, selenium-containing groups, phosphor-containing groups, andcyano groups, wherein N, O, S, Se and P in E each represents acoordination atom; G is chosen from the group consisting of C₁-C₃₀hydrocarbylene groups, substituted C₁-C₃₀ hydrocarbylene groups, andinert functional groups; → represents a single bond or a double bond; -represents a covalent bond or an ionic bond; --- represents acoordination bond, a covalent bond or an ionic bond; R¹ to R³, R²² toR³³, and R³⁹ are each independently chosen from the group consisting ofa hydrogen atom, C₁-C₃₀ hydrocarbyl groups, substituted C₁-C₃₀hydrocarbyl groups, and inert functional groups, wherein these groupsmay be identical to or different from one another, and any adjacentgroups may form a bond or a ring with one another.
 2. A process forproducing a supported nonmetallocene catalyst, comprising: dissolving atleast one magnesium compound and at least one nonmetallocene complex inat least one solvent to obtain a magnesium compound solution; mixing atleast one carrier chosen from the group consisting of porous carriersand thermally activated porous carriers with the magnesium compoundsolution to obtain a slurry; drying the slurry or introducing into theslurry at least one precipitating agent to obtain a composite carrier;and treating the composite carrier with at least one chemical treatingagent chosen from the group consisting of Group IVB metal compounds toobtain the supported nonmetallocene catalyst, wherein the nonmetallocenecomplex is chosen from the group consisting of the compounds havingfollowing formula,

wherein: q is 0 or 1; d is 1; m is 1, 2 or 3; M is chosen from the groupconsisting of metal atoms of Groups III to XI; n is 1, 2, 3 or 4; X ischosen from the group consisting of halogen atoms, a hydrogen atom,C₁-C₃₀ hydrocarbyl groups, substituted C₁-C₃₀ hydrocarbyl groups,oxygen-containing groups, nitrogen-containing groups, sulfur-containinggroups, boron-containing groups, aluminum-containing groups,phosphor-containing groups, silicon-containing groups,germanium-containing groups, and tin-containing groups, when multiple Xsexist, the Xs may be the same as or different from one another, and mayform a bond or a ring with one another; A is chosen from the groupconsisting of an oxygen atom, a sulfur atom, a selenium atom,

—NR²³R²⁴,

—PR²⁸R²⁹, —P(O)R³⁰OR³¹, sulfone groups, sulfoxide groups, and —Se(O)R³⁹,wherein N, O, S, Se and P in A each represents a coordination atom; B ischosen from the group consisting of a nitrogen atom, nitrogen-containinggroups, phosphor-containing groups, and C₁-C₃₀ hydrocarbylene groups; Dis chosen from the group consisting of a nitrogen atom, an oxygen atom,a sulfur atom, a selenium atom, a phosphor atom, nitrogen-containinggroups, phosphor-containing groups, C₁-C₃₀ hydrocarbylene group, sulfonegroup, sulfoxide groups,

and —P(O)R³²(OR³³), wherein N, O, S, Se and P in D each represents acoordination atom; E is chosen from the group consisting ofnitrogen-containing groups, oxygen-containing groups, sulfur-containinggroups, selenium-containing groups, phosphor-containing groups, andcyano groups, wherein N, O, S, Se and P in E each represents acoordination atom; G is chosen from the group consisting of C₁-C₃₀hydrocarbylene groups, substituted C₁-C₃₀ hydrocarbylene groups, andinert functional groups; → represents a single bond or a double bond; -represents a covalent bond or an ionic bond; --- represents acoordination bond, a covalent bond or an ionic bond; R¹ to R³, R²² toR³³, and R³⁹ are each independently chosen from the group consisting ofa hydrogen atom, C₁-C₃₀ hydrocarbyl groups, substituted C₁-C₃₀hydrocarbyl groups, and inert functional groups, wherein these groupsmay be identical to or different from one another, and any adjacentgroups may form a bond or a ring with one another.
 3. The processaccording to claim 2, further comprising pre-treating the compositecarrier with at least one assistant chemical treating agent chosen fromthe group consisting of aluminoxanes and alkylaluminums before treatingthe composite carrier with the at least one chemical treating agent. 4.The process according to claim 1 or 2, wherein the at least one carrieris chosen from the group consisting of olefin homopolymers orcopolymers, vinyl alcohol homopolymers or copolymers, cyclodextrins,polyesters or co-polyesters, polyamides or co-polyamides, vinyl chloridehomopolymers or copolymers, acrylic ester homopolymers or copolymers,methacrylic ester homopolymers or copolymers, styrene homopolymers orcopolymers, partly crosslinked products of these homopolymers orcopolymers, refractory oxides or refractory composite oxides of a GroupIIA, IIIA, IVA or IVB metal, clay, molecular sieve, mica,montmorillonite, bentonite and kieselguhr.
 5. The process according toclaim 4, wherein the at least one is chosen from the group consisting ofpartly crosslinked styrene polymers, silica, alumina, magnesia,silica-alumina, magnesia-alumina, titanium oxide, molecular sieve andmontmorillonite.
 6. The process according to claim 1 or 2, wherein theat least one magnesium compound is chosen from the group consisting ofmagnesium halides, alkoxy magnesium halides, alkoxy magnesiums, alkylmagnesiums, alkyl magnesium halides and alkyl alkoxy magnesiums.
 7. Theprocess according to claim 6, wherein the at least one magnesiumcompound is chosen from the group consisting of magnesium halides. 8.The process according to claim 1 or 2, wherein the at least one solventis chosen from the group consisting of C₆₋₁₂ aromatic hydrocarbons,halogenated C₆₋₁₂ aromatic hydrocarbons, esters and ethers.
 9. Theprocess according to claim 1 or 2, wherein the at least onenonmetallocene complex is chosen from the group consisting of compound(A) and compound (B),

wherein, F is chosen from the group consisting of a nitrogen atom,nitrogen-containing groups, oxygen-containing groups, sulfur-containinggroups, selenium-containing groups and phosphor-containing groups,wherein N, O, S, Se and P in F each represents a coordination atom. 10.The process according to claim 9, wherein the at least onenonmetallocene complex is chosen from the group consisting of compound(A-1), compound (A-2), compound (A-3), compound (A-4), compound (B-1),compound (B-2), compound (B-3), and compound (B-4),

wherein, Y is chosen from the group consisting of an oxygen atom,nitrogen-containing groups, oxygen-containing groups, sulfur-containinggroups, selenium-containing groups and phosphor-containing groups,wherein N, O, S, Se and P in Y each represents a coordination atom; Z ischosen from the group consisting of nitrogen-containing groups,oxygen-containing groups, sulfur-containing groups, selenium-containinggroups, phosphor-containing groups and cyano groups, wherein N, O, S, Seand P in Z each represents a coordination atom; R⁴, and R⁶ to R²¹ areeach independently chosen from the group consisting of a hydrogen atom,C₁-C₃₀ hydrocarbyl groups, substituted C₁-C₃₀ hydrocarbyl groups andinert functional groups, wherein these groups may be identical to ordifferent from one another, and any adjacent groups may form a bond or aring with one another; and R⁵ is chosen from the group consisting of alone pair electron on a nitrogen atom, a hydrogen atom, C₁-C₃₀hydrocarbyl groups, substituted C₁-C₃₃ hydrocarbyl groups,oxygen-containing groups, sulfur-containing groups, nitrogen-containinggroups, selenium-containing groups, and phosphor-containing groups, withthe proviso that when R⁵ is chosen from the group consisting ofoxygen-containing groups, sulfur-containing groups, nitrogen-containinggroups, selenium-containing groups and phosphor-containing groups, N, O,S, P and Se in the R⁵ each can act as a coordination atom.
 11. Theprocess according to claim 10, wherein, the halogen atom is chosen fromthe group consisting of F, Cl, Br and I, the nitrogen-containing groupsare chosen from the group consisting of

—NR²³R²⁴, and -T-NR²³R²⁴, the phosphor-containing groups are chosen fromthe group consisting of

—PR²⁸R²⁹, —P(O)R³⁰R³¹ and —P(O)R³²(OR³³), the oxygen-containing groupsare chosen from the group consisting of hydroxy, —OR³⁴ and -T-OR³⁴, thesulfur-containing groups are chosen from the group consisting of —SR³⁵,-T-SR³⁵, —S(O)R³⁶ and -T-SO₂R³⁷, the selenium-containing groups arechosen from the group consisting of —SR³⁸, -T-SeR³⁸, —Se(O)R³⁹ and-T-Se(O)R³⁹, the group T is chosen from the group consisting of C₁-C₃₀hydrocarbylene groups, substituted C₁-C₃₀ hydrocarbylene groups andinert functional groups, R³⁷ is chosen from the group consisting of ahydrogen atom, C₁-C₃₀ hydrocarbyl groups, substituted C₁-C₃₀ hydrocarbylgroups and inert functional groups, the C₁-C₃₀ hydrocarbyl groups arechosen from the group consisting of C₁-C₃₀ alkyl groups, C₇-C₅₀alkylaryl groups, C₇-C₅₀ aralkyl groups, C₃-C₃₀ cyclic alkyl groups,C₂-C₃₀ alkenyl groups, C₂-C₃₀ alkynyl groups, C₆-C₃₀ aryl groups, C₈-C₃₀fused-ring groups and C₄-C₃₀ heterocycle groups, wherein the C₄-C₃₀heterocycle group contains 1 to 3 hetero atom(s) chosen from the groupconsisting of a nitrogen atom, an oxygen atom and a sulfur atom, thesubstituted C₁-C₃₀ hydrocarbyl groups are chosen from the groupconsisting of hydrocarbyl groups having at least one substituent chosenfrom the group consisting of halogen atoms and C₁-C₃₀ alkyl groups, theinert functional groups are chosen from the group consisting of halogenatoms, oxygen-containing groups, nitrogen-containing groups,silicon-containing groups, germanium-containing groups,sulfur-containing groups, tin-containing groups, C₁-C₁₀ ester groups andnitro groups, the boron-containing groups are chosen from the groupconsisting of BF₄ ⁻, (C₆F₅)₄B⁻ and (R⁴⁰BAr₃)⁻, the aluminum-containinggroups are chosen from the group consisting of AlPh₄ ⁻, AlBr₄ ⁻, AlCl₄⁻, AlBr₄ ⁻, AlI₄ ⁻ and R⁴¹AlAr₃ ⁻, the silicon-containing groups arechosen from the group consisting of —SiR⁴²R⁴³R⁴⁴, and -T-SiR⁴⁵, thegermanium-containing groups are chosen from the group consisting of—GeR⁴⁶R⁴⁷R⁴⁸ and -T-GeR⁴⁹, the tin-containing groups are chosen from thegroup consisting of —SnR⁵⁰R⁵¹R⁵², -T-SnR⁵³ and -T-Sn(O)R⁵⁴, the Ar ischosen from the group consisting of C₆-C₃₀ aryl groups, R³⁴ to R³⁶, R³⁸and R⁴⁰ to R⁵⁴ are each independently chosen from the group consistingof a hydrogen atom, C₁-C₃₀ hydrocarbyl groups, substituted C₁-C₃₀hydrocarbyl groups and inert functional groups, wherein these groups maybe identical to or different from one another, and any adjacent groupsmay form a bond or a ring with one another.
 12. The process according toclaim 1 or 2, wherein the at least one nonmetallocene complex is chosenfrom the group consisting of:


13. The process according to claim 1, wherein molar ratio of the atleast one magnesium compound (based on Mg) to the at least onenonmetallocene complex is 1:0.01-1, ratio of the at least one magnesiumcompound to the at least one solvent is 1 mol:75-400 ml, weight ratio ofthe at least one magnesium compound (on a solid basis) to the at leastone carrier is 1:0.1-20, and volume ratio of the at least oneprecipitating agent to the at least one solvent is 1:0.2-5.
 14. Theprocess according to claim 2, wherein molar ratio of the at least onemagnesium compound (based on Mg) to the at least one nonmetallocenecomplex is 1:0.01-1, ratio of the at least one magnesium compound to theat least one solvent is 1 mol:75-400 ml, weight ratio of the at leastone magnesium compound (on a solid basis) to the at least one carrier is1:0.1-20, volume ratio of the at least one precipitating agent to the atleast one solvent is 1:0.2-5, and molar ratio of the at least onemagnesium compound (based on Mg) to the at least one chemical treatingagent (based on the Group IVB metal) is 1:0.01-1.
 15. The processaccording to claim 1 or 2, wherein the at least one precipitating agentis chosen from the group consisting of alkanes, cyclic alkanes,halogenated alkanes and halogenated cyclic alkanes.
 16. The processaccording to claim 15, wherein the at least one precipitating agent ischosen from the group consisting of pentane, hexane, heptane, octane,nonane, decane, cyclohexane, cyclopentane, cycloheptane, cyclodecane,cyclononane, dichloromethane, dichloro hexane, dichloro heptane,trichloro methane, trichloro ethane, trichloro butane, dibromo methane,dibromo ethane, dibromo heptane, tribromo methane, tribromo ethane,tribromo butane, chlorinated cyclopentane, chlorinated cyclohexane,chlorinated cycloheptane, chlorinated cyclooctane, chlorinatedcyclononane, chlorinated cyclodecane, brominated cyclopentane,brominated cyclohexane, brominated cycloheptane, brominated cyclooctane,brominated cyclononane and brominated cyclodecane.
 17. The processaccording to claim 2, wherein the Group IVB metal compounds are chosenfrom the group consisting of Group IVB metal halides, Group IVB metalalkylates, Group IVB metal alkoxylates, Group IVB metal alkyl halides,and Group IVB metal alkoxy halides.
 18. The process according to claim17, wherein the Group IVB metal compounds are chosen from the groupconsisting of Group IVB metal halides.
 19. The process according toclaim 3, wherein the aluminoxanes are chosen from the group consistingof methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane andn-butyl aluminoxane, and the alkylaluminum is one or more selected fromthe group consisting of trimethyl aluminum, triethyl aluminum, tripropylaluminum, triisobutyl aluminum, tri-n-butyl aluminum, triisoamylaluminum, tri-n-amyl aluminum, trihexyl aluminum, tri-iso-hexylaluminum, diethyl methyl aluminum and ethyl dimethyl aluminum.
 20. Theprocess according to claim 3, wherein molar ratio of the at least onemagnesium compound (based on Mg) to the at least one assistant chemicaltreating agent (based on Al) is 1:0-1.0.
 21. A supported nonmetallocenecatalyst, produced according to the process of claim 1 or
 2. 22. Anolefin homopolymerization/copolymerization process comprisingpolymerizing at least one olefin in the presence of the supportednonmetallocene catalyst according to claim 21 with at least oneco-catalyst chosen from the group consisting of aluminoxanes,alkylaluminums, halogenated alkyl aluminums, fluoroboranes, alkylboronsand alkylboron ammonium salts.